Compositions comprising a fluoroolefin

ABSTRACT

The present invention relates to compositions for use in refrigeration, air-conditioning, and heat pump systems wherein the composition comprises a fluoroolefin and at least one other component. The compositions of the present invention are useful in processes for producing cooling or heat, as heat transfer fluids, foam blowing agents, aerosol propellants, and fire suppression and fire extinguishing agents.

CROSS REFERENCE(S) TO RELATED APPLICATION(S)

This application claims the priority benefit of and is a divisional ofU.S. patent application Ser. No. 11/486,791, filed Jul. 13, 2006, nowgranted as U.S. Pat. No. 7,569,170, which is a continuation-in-part ofU.S. patent application Ser. No. 11/393,109, filed Mar. 30, 2006, nowabandoned, which is a continuation-in-part of and claims the prioritybenefit of U.S. patent application Ser. No. 11/369,227, filed Mar. 2,2006, now abandoned, which claims the priority benefit of U.S.Provisional Application 60/658,543, filed Mar. 4, 2005, and U.S.Provisional Application 60/710,439, filed Aug. 23, 2005, and U.S.Provisional Application 60/732,769, filed Nov. 1, 2005.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to compositions for use in refrigeration,air-conditioning, and heat pump systems wherein the compositioncomprises a fluoroolefin and at least one other component. Thecompositions of the present invention are useful in processes forproducing cooling or heat, as heat transfer fluids, foam blowing agents,aerosol propellants, and fire suppression and fire extinguishing agents.

2. Description of Related Art

The refrigeration industry has been working for the past few decades tofind replacement refrigerants for the ozone depletingchlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) beingphased out as a result of the Montreal Protocol. The solution for mostrefrigerant producers has been the commercialization ofhydrofluorocarbon (HFC) refrigerants. The new HFC refrigerants, HFC-134abeing the most widely used at this time, have zero ozone depletionpotential and thus are not affected by the current regulatory phase outas a result of the Montreal Protocol.

Further environmental regulations may ultimately cause global phase outof certain HFC refrigerants. Currently, the automobile industry isfacing regulations relating to global warming potential for refrigerantsused in mobile air-conditioning. Therefore, there is a great currentneed to identify new refrigerants with reduced global warming potentialfor the mobile air-conditioning market. Should the regulations be morebroadly applied in the future, an even greater need will be felt forrefrigerants that can be used in all areas of the refrigeration andair-conditioning industry.

Currently proposed replacement refrigerants for HFC-134a includeHFC-152a, pure hydrocarbons such as butane or propane, or “natural”refrigerants such as CO₂. Many of these suggested replacements aretoxic, flammable, and/or have low energy efficiency. Therefore, newalternative refrigerants are being sought.

The object of the present invention is to provide novel refrigerantcompositions and heat transfer fluid compositions that provide uniquecharacteristics to meet the demands of low or zero ozone depletionpotential and lower global warming potential as compared to currentrefrigerants.

BRIEF SUMMARY OF THE INVENTION

The present invention relates to a composition comprising HFC-1225ye andat least one compound selected from the group consisting of: HFC-1234ze,HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a,HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa,HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane,cyclopentane, dimethylether, CF₃SCF₃, CO₂, NH₃ and CF₃I.

The present invention further relates to a composition comprisingHFC-1234ze and at least one compound selected from the group consistingof: HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134,HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa,HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane,n-pentane, cyclopentane, dimethylether, CF₃SCF₃, CO₂, NH₃ and CF₃I. Thepresent invention further relates to a composition comprising HFC-1234yfand at least one compound selected from the group consisting of:HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a,HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa,HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane,cyclopentane, dimethylether, CF₃SCF₃, CO₂ and CF₃I.

The present invention further relates to a composition comprisingHFC-1234ye and at least one compound selected from the group consistingof: HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a,HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc,propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane,dimethylether, CF₃SCF₃, CO₂ and CF₃I.

The present invention further relates to a composition comprisingHFC-1243zf and at least one compound selected from the group consistingof: HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161,HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane,n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane,dimethylether, CF₃SCF₃, CO₂ and CF₃I.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to compositions comprising at least onefluoroolefin. The compositions of the present invention further compriseat least one additional component that may be a second fluoroolefin,hydrofluorocarbon (HFC), hydrocarbon, dimethyl ether,bis(trifluoromethyl)sulfide, CF₃I, or CO₂. The fluoroolefin compoundsand other components of the present inventive compositions are listed inTable 1.

TABLE 1 Compound Chemical name Chemical formula HFC-1225ye1,2,3,3,3-pentafluoropropene CF₃CF═CHF HFC-1234ze1,3,3,3-tetrafluoropropene CF₃CH═CHF HFC-1234yf2,3,3,3-tetrafluoropropene CF₃CF═CH₂ HFC-1234ye1,2,3,3-tetrafluoropropene CHF₂CF═CHF HFC-1243zf 3,3,3-trifluoropropeneCF₃CH═CH₂ HFC-32 difluoromethane CH₂F₂ HFC-125 pentafluoroethane CF₃CHF₂HFC-134 1,1,2,2-tetrafluoroethane CHF₂CHF₂ HFC-134a1,1,1,2-tetrafluoroethane CH₂FCF₃ HFC-143a 1,1,1-trifluoroethane CH₃CF₃HFC-152a 1,1-difluoroethane CHF₂CH₃ HFC-161 fluoroethane CH₃CH₂FHFC-227ea 1,1,1,2,3,3,3- CF₃CHFCF₃ heptafluoropropane HFC-236ea1,1,1,2,3,3-hexafluoropropane CF₃CHFCHF₂ HFC-236fa1,1,1,3,3,3-hexafluoroethane CF₃CH₂CF₃ HFC-245fa1,1,1,3,3-pentafluoropropane CF₃CH₂CHF₂ HFC-365mfc1,1,1,3,3-pentafluorobutane CF₃CH₂CH₂CHF₂ Propane CH₃CH₂CH₃ n-butaneCH₃CH₂CH₂CH₃ i-butane isobutane CH₃CH(CH₃)CH₃ 2-methylbutaneCH₃CH(CH₃)CH₂CH₃ n-pentane CH₃CH₂CH₂CH₂CH₃ cyclopentane cyclo-(CH₂)₅—DME dimethylether CH₃OCH₃ CO₂ carbon dioxide CO₂ CF₃SCF₃bis(trifluoromethyl)sulfide CF₃SCF₃ iodotrifluoromethane CF₃I NH₃Ammonia NH₃

The individual components listed in Table 1 may be prepared by methodsknown in the art.

The fluoroolefin compounds used in the compositions of the presentinvention, HFC-1225ye, HFC-1234ze, and HFC-1234ye, may exist asdifferent configurational isomers or stereoisomers. The presentinvention is intended to include all single configurational isomers,single stereoisomers or any combination or mixture thereof. Forinstance, 1,3,3,3-tetra-fluoropropene (HFC-1234ze) is meant to representthe cis-isomer, trans-isomer, or any combination or mixture of bothisomers in any ratio. Another example is HFC-1225ye, by which isrepresented the cis-isomer, trans-isomer, or any combination or mixtureof both isomers in any ratio. The compositions of the present inventioncontain primarily the cis or Z isomer of HFC-1225ye.

The compositions of the present invention include the following:

HFC-1225ye and at least one compound selected from the group consistingof HFC-1234ze, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125,HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea,HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane,2-methylbutane, n-pentane, cyclopentane, dimethylether, CF₃SCF₃, CO₂,NH₃, and CF₃I;

HFC-1234ze and at least one compound selected from the group consistingof HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134,HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa,HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane,n-pentane, cyclopentane, dimethylether, CF₃SCF₃, CO₂ and CF₃I;

HFC-1234yf and at least one compound selected from the group consistingof HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a,HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa,HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane,cyclopentane, dimethylether, CF₃SCF₃, CO₂, NH₃, and CF₃I;

HFC-1243zf and at least one compound selected from the group consistingof HFC-1234ye, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a,HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc,propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane,dimethylether, CF₃SCF₃, CO₂ and CF₃I; and

HFC-1234ye and at least one compound selected from the group consistingof HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a,HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc,propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane,dimethylether, CF₃SCF₃, CO₂ and CF₃I.

The compositions of the present invention may be generally useful whenthe fluoroolefin is present at about 1 weight percent to about 99 weightpercent, preferably about 20 weight percent to about 99 weight percent,more preferably about 40 weight percent to about 99 weight percent andstill more preferably 50 weight percent to about 99 weight percent.

The present invention further provides compositions as listed in Table2.

TABLE 2 Concentration ranges (wt %) Components Preferred More preferredMost preferred HFC-1225ye/HFC-32 1-99/99-1 30-99/70-1 90-99/10-1;95/5/97/3 HFC-1225ye/HFC-134a 1-99/99-1 40-99/60-1 90/10 HFC-1225ye/CO₂0.1-99.9/99.9-0.1 70-99.7/30-0.3 99/1 HFC-1225ye/ammonia0.1-99.9/0.1-99.9 40-99.9/0.1-60 90/10, 85/15, 80/ 20, 95/5HFC-1225ye/HFC-1234yf 1-99/99-1 51-99/49-1 and 60-90/ 60/40, 51/49 40-10HFC-1225ye/HFC-152a/HFC-32 1-98/1-98/1-98 50-98/1-40/1-40 85/10/581/15/4 82/15/3 HFC-1225ye/HFC-152a/CO₂ 1-98/1-98/0.1-9850-98/1-40/0.3-30 84/15/1 84/15.5/0.5 HFC-1225ye/HFC-152a/propane1-98/1-98/1-98 50-98/1-40/1-20 85/13/2 HFC-1225ye/HFC-152a/i-butane1-98/1-98/1-98 50-98/1-40/1-20 85/13/2 HFC-1225ye/HFC-152a/DME1-98/1-98/1-98 50-98/1-40/1-20 85/13/2 HFC-1225ye/HFC-152a/CF₃I1-98/1-98/1-98 20-90/1-50/1-60 HFC-1225ye/HFC-134a/HFC- 1-98/1-98/1-9840-98/1-50/1-40 76/9/15 152a HFC-1225ye/HFC-134a/HFC-32 1-98/1-98/1-981-80/1-80/1-80 88/9/3 HFC-1225ye/HFC-134a/HFC-161 1-98/1-98/1-9840-98/1-50/1-20 86/10/4 HFC-1225ye/HFC-134a/CO₂ 1-98/1-98/0.1-9840-98/1-50/0.3-30 88.5/11/0.5 HFC-1225ye/HFC-134a/propane 1-98/1-98/1-9840-98/1-50/1-20 87/10/3 HFC-1225ye/HFC-134a/i-butane 1-98/1-98/1-9840-98/1-50/1-20 87/10/3 HFC-1225ye/HFC-134a/DME 1-98/1-98/1-9840-98/1-50/1-20 87/10/3 HFC-1225ye/HFC-134/HFC-32 1-98/1-98/1-9840-98/1-50/1-40 88/9/3 trans-HFC-1234ze/HFC-134a 1-99/99-1 30-99/70-190/10 trans-HFC-1234ze/HFC-32 1-99/99-1 40-99/60-1 95/5trans-HFC-1234ze/HFC-32/CF₃I 1-98/1-98/1-98 20-90/0.1-60/1-70trans-HFC-1234ze/HFC-152a 1-99/99-1 40-99/60-1 80/20trans-HFC-1234ze/HFC-125 1-99/99-1 30-99/70-1 HFC-1234yf/HFC-134a1-99/99-1 30-99/70-1 90/10 HFC-1234yf/HFC-32 1-99/99-1 40-99/60-1 95/5HFC-1234yf/HFC-125 0.1-99/99-0.1 40-99/1-60 HFC-1234yf/HFC-152a1-99/99-1 40-99/60-1 80/20 HFC-1225ye/HFC-134a/HFC- 1-97/1-97/1-97/20-97/1-80/1-50/ 74/8/17/1 152a/HFC-32 0.1-97 0.1-50HFC-1225ye/HFC-1234yf/HFC- 1-98/1-98/0.1-98 10-90/10-90/0.1-50 70/20/10and 134a 20/70/10 HFC-1225ye/HFC-1234yf/HFC-32 1-98/1-98/0.1-9810-90/5-90/0.1-50 25/73/2, 75/23/2, 49/49/2, 85/10/5, 90/5/5HFC-1225ye/HFC-1234yf/HFC- 1-97/1-97/0.1-97/ 10-80/10-80/1-60/1-6032/CF₃I 1-97 HFC-1225ye/HFC-1234yf/HFC- 1-98/1-98/0.1-9810-90/10-90/0.1-50 70/25/5 and 152a 25/70/5 HFC-1225ye/HFC-1234yf/HFC-1-98/1-98/0.1-98 10-90/10-90/0.1-50 25/71/4, 125 75/21/4, 75/24/1 and25/74/1 HFC-1225ye/HFC-1234yf/CF₃I 1-98/1-98/1-98 9-90/9-90/1-6040/40/20 and 45/45/10 HFC-32/HFC-125/HFC-1225ye 0.1-98/0.1-98/5-70/5-70/5-70 30/30/40 and 0.1-98 23/25/52 HFC-32/HFC-125/trans-HFC-0.1-98/0.1-98/ 5-70/5-70/5-70 30/50/20 and 1234ze 0.1-98 23/25/52HFC-32/HFC-125/HFC-1234yf 0.1-98/0.1-98/ 5-70/5-70/5-70 40/50/10, 0.1-9823/25/52, 15/45/40, and 10/60/30 HFC-32/HFC-134a/HFC- 1-97/1-97/1-97/1-60/1-60/1-60/1-60 1225ye/CF₃I 1-97 HFC-32/HFC-134a/HFC-1-96/1-96/1-96/ 1-50/1-50/1-50/1-50/ 1225ye/HFC-1234yf/CF₃I 1-96/1-961-50 HFC-32/HFC-125/HFC- 1-96/1-96/1-96/ 1-50/1-50/1-50/1-50/134a/HFC-1225ye/CF₃I 1-96/1-96 1-50 HFC-125/HFC-1225ye/n-butane0.1-98/0.1-98/ 5-70/5-70/1-20 65/32/3 and 0.1-98 85.1/11.5/3.4HFC-32/NH₃/HFC-1225ye 1-98/1-98/1-98 1-60/10-60/10-90HFC-32/NH₃/HFC-1225ye/CF₃I 1-97/1-97/1-97/ 1-60/1-60/10-80/1-60 1-97HFC-32/NH₃/HFC-1234yf/CF₃I 1-97/1-97/1-97/ 1-60/1-60/10-80/5-80 1-97HFC-125/trans-HFC-1234ze/n- 0.1-98/0.1-98/ 5-70/5-70/1-20 66/32/2 andbutane 0.1-98 86.1/11.5/2.4 HFC-125/HFC-1234yf/n-butane 0.1-98/0.1-98/5-70/5-70/1-20 67/32/1 and 0.1-98 87.1/11.5/1.4HFC-125/HFC-1225ye/isobutane 0.1-98/0.1-98/ 5-70/5-70/1-20 85.1/11.5/3.40.1-98 and 65/32/3 HFC-1225ye/HFC-125/ammonia 0.1-98/0.1-98/20-98/1-60/0.1-40 0.1-98 HFC-1225ye/HFC-32/HFC- 0.1-97/0.1-97/20-97/1-60/1-60/ 125/ammonia 0.1-97/0.1-97 0.1-40 HFC-125/trans-HFC-0.1-98/0.1-98/ 5-70/5-70/1-20 86.1/11.5/2.4 1234ze/isobutane 0.1-98 and66/32/2 HFC-125/HFC-1234yf/isobutane 0.1-98/0.1-98/ 5-70/5-70/1-20 and87.1/11.5/1.4 0.1-98 80-98/1-19/1-10 and 67/32/1HFC-1234yf/HFC-32/HFC-143a 1-50/1-98/1-98 15-50/20-80/5-60HFC-1234yf/HFC-32/isobutane 1-40/59-98/1-30 10-40/59-90/1-10HFC-1234yf/HFC-125/HFC-143a 1-60/1-98/1-98 10-60/20-70/20-70HFC-1234yf/HFC-125/isobutane 1-40/59-98/1-20 10-40/59-90/1-10HFC-1234yf/HFC-125/CF₃I 1-98/0.1-98/1-98 10-80/1-60/1-60HFC-1234yf/HFC-134/propane 1-80/1-70/19-90 20-80/10-70/19-50HFC-1234yf/HFC-134/DME 1-70/1-98/29-98 20-70/10-70/29-50HFC-1234yf/HFC-134a/propane 1-80/1-80/19-98 10-80/10-80/19-50HFC-1234yf/HFC-134a/n-butane 1-98/1-98/1-30 10-80/10-80/1-20HFC-1234yf/HFC-134a/isobutane 1-98/1-98/1-30 10-80/10-80/1-20HFC-1234yf/HFC-134a/DME 1-98/1-98/1-40 10-80/10-80/1-20HFC-1234yf/HFC-134a/CF₃I 1-98/1-98/1-98 10-80/1-60/1-60HFC-1234yf/HFC-143a/propane 1-80/1-98/1-98 10-80/10-80/1-50HFC-1234yf/HFC-143a/DME 1-40/59-98/1-20 5-40/59-90/1-10HFC-1234yf/HFC-152a/n-butane 1-98/1-98/1-30 10-80/10-80/1-20HFC-1234yf/HFC-152a/isobutane 1-98/1-90/1-40 10-80/10-80/1-20HFC-1234yf/HFC-152a/DME 1-70/1-98/1-98 10-70/10-80/1-20HFC-1234yf/HFC-152a/CF₃I 1-98/1-98/1-98 10-80/1-60/1-60HFC-1234yf/HFC-227ea/propane 1-80/1-70/29-98 10-60/10-60/29-50HFC-1234yf/HFC-227ea/n-butane 40-98/1-59/1-20 50-98/10-49/1-10HFC-1234yf/HFC- 30-98/1-69/1-30 50-98/10-49/1-10 227ea/isobutaneHFC-1234yf/HFC-227ea/DME 1-98/1-80/1-98 10-80/10-80/1-20HFC-1234yf/n-butane/DME 1-98/1-40/1-98 10-80/10-40/1-20HFC-1234yf/isobutane/DME 1-98/1-50/1-98 10-90/1-40/1-20HFC-1234yf/DME/CF₃I 1-98/1-98/1-98 10-80/1-20/10-80HFC-1234yf/DME/CF₃SCF₃ 1-98/1-40/1-98 10-80/1-20/10-70HFC-1225ye/trans-HFC- 1-98/1-98/1-98 10-80/10-80/10-80 1234ze/HFC-134HFC-1225ye/trans-HFC- 1-98/1-98/1-98 10-80/10-80/10-80 1234ze/HFC-227eaHFC-1225ye/trans-HFC- 1-60/1-60/39-98 10-60/10-60/39-80 1234ze/propaneHFC-1225ye/trans-HFC- 1-98/1-98/1-30 10-80/10-80/1-20 1234ze/n-butaneHFC-1225ye/trans-HFC- 1-98/1-98/1-98 10-80/10-80/1-30 1234ze/DMEHFC-1225ye/trans-HFC-1234ze/ 1-98/1-98/1-98 10-80/10-80/10-80 CF₃SCF₃HFC-1225ye/HFC-1243zf/HFC- 1-98/1-98/1-98 10-80/10-80/10-80 134HFC-1225ye/HFC-1243zf/n- 1-98/1-98/1-30 10-80/10-80/1-20 butaneHFC-1225ye/HFC- 1-98/1-98/1-40 10-80/10-80/1-30 1243zf/isobutaneHFC-1225ye/HFC-1243zf/DME 1-98/1-98/1-98 10-80/10-80/1-30HFC-1225ye/HFC-1243zf/CF₃I 1-98/1-98/1-98 10-80/10-80/10-80HFC-1225ye/HFC-134/HFC-152a 1-98/1-98/1-98 10-80/10-80/1-50HFC-1225ye/HFC-134/HFC- 1-98/1-98/1-98 10-80/10-80/10-80 227eaHFC-1225ye/HFC-134/n-butane 1-98/1-90/1-40 10-80/10-80/1-30HFC-1225ye/HFC-134/isobutane 1-98/1-90/1-40 10-80/10-80/1-30HFC-1225ye/HFC-134/DME 1-98/1-98/1-40 10-80/10-80/1-30HFC-1225ye/HFC-227ea/DME 40-98/1-59/1-30 50-98/1-49/1-20HFC-1225ye/n-butane/DME 1-98/1-30/1-98 60-98/1-20/1-20HFC-1225ye/n-butane/CF₃SCF₃ 1-98/1-20/1-98 10-80/1-10/10-80HFC-1225ye/isobutane/DME 1-98/1-60/1-98 40-90/1-30/1-30HFC-1225ye/isobutane/CF₃I 1-98/1-40/1-98 10-80/1-30/10-80trans-HFC-1234ze/HFC- 1-98/1-98/1-98 10-80/10-80/10-80 1243zf/HFC-227eatrans-HFC-1234ze/HFC-1243zf/n- 1-98/1-98/1-30 10-80/10-80/1-20 butanetrans-HFC-1234ze/HFC- 1-98/1-98/1-40 10-80/10-80/1-30 1243zf/isobutanetrans-HFC-1234ze/HFC- 1-98/1-98/1-98 10-80/10-80/1-40 1243zf/DMEtrans-HFC-1234ze/HFC-32/CF3I 1-98/1-98/1-98 10-80/1-70/1-80trans-HFC-1234ze/HFC- 1-98/1-98/1-98 10-80/10-80/1-50 134/HFC-152atrans-HFC-1234ze/HFC- 1-98/1-98/1-98 10-80/10-80/10-80 134/HFC-227eatrans-HFC-1234ze/HFC-134/DME 1-98/1-98/1-40 10-80/10-80/1-30trans-HFC-1234ze/HFC- 1-98/1-98/1-98 10-80/10-80/1-50 134a/HFC-152atrans-HFC-1234ze/HFC-152a/n- 1-98/1-98/1-50 10-80/10-80/1-30 butanetrans-HFC-1234ze/HFC- 1-98/1-98/1-98 20-90/1-50/1-30 152a/DMEtrans-HFC-1234ze/HFC-227ea/n- 1-98/1-98/1-40 10-80/10-80/1-30 butanetrans-HFC-1234ze/n-butane/DME 1-98/1-40/1-98 10-90/1-30/1-30trans-HFC-1234ze/n-butane/CF₃I 1-98/1-30/1-98 10-80/1-20/10-80trans-HFC- 1-98/1-60/1-98 10-90/1-30/1-30 1234ze/isobutane/DMEtrans-HFC-1234ze/isobutane/ 1-98/1-40/1-98 10-80/1-20/10-80 CF₃Itrans-HFC-1234ze/isobutane/ 1-98/1-40/1-98 10-80/1-20/10-80 CF₃SCF₃HFC-1243zf/HFC-134/HFC- 1-98/1-98/1-98 10-80/10-80/10-80 227eaHFC-1243zf/HFC-134/n-butane 1-98/1-98/1-40 10-80/10-80/1-30HFC-1243zf/HFC-134/DME 1-98/1-98/1-98 10-80/10-80/1-30HFC-1243zf/HFC-134/CF₃I 1-98/1-98/1-98 10-80/10-80/10-80HFC-1243zf/HFC-134a/HFC- 1-98/1-98/1-98 10-80/10-80/1-50 152aHFC-1243zf/HFC-134a/n-butane 1-98/1-98/1-40 10-80/10-80/1-30HFC-1243zf/HFC-152a/propane 1-70/1-70/29-98 10-70/1-50/29-40HFC-1243zf/HFC-152a/n-butane 1-98/1-98/1-30 10-80/1-80/1-20HFC-1243zf/HFC-152a/isobutane 1-98/1-98/1-40 10-80/1-80/1-30HFC-1243zf/HFC-152a/DME 1-98/1-98/1-98 10-80/1-80/1-30HFC-1243zf/HFC-227ea/n-butane 1-98/1-98/1-40 10-80/1-80/1-30HFC-1243zf/HFC- 1-98/1-90/1-50 10-80/1-80/1-30 227ea/isobutaneHFC-1243zf/HFC-227ea/DME 1-98/1-80/1-90 10-80/1-80/1-30HFC-1243zf/n-butane/DME 1-98/1-40/1-98 10-90/1-30/1-30HFC-1243zf/isobutane/DME 1-98/1-60/1-98 10-90/1-30/1-30HFC-1243zf/isobutane/CF₃I 1-98/1-40/1-98 10-80/1-30/10-80HFC-1243zf/DME/CF₃SCF₃ 1-98/1-40/1-90 10-80/1-30/10-80HFC-1225ye/HFC-32/CF₃I 1-98/1-98/1-98 5-80/1-70/1-80HFC-1225ye/HFC-1234yf/HFC- 1-97/1-97/1-97/ 1-80/1-70/5-70/5-7032/HFC-125 1-97 HFC-1225ye/HFC-1234yf/HFC- 1-97/1-97/1-97/5-80/5-70/5-70/5-70 32/HFC-134a 1-97 HFC-1225ye/HFC-1234yf/HFC-1-96/1-96/1-96/ 1-70/1-60/1-70/1-60/ 32/HFC-125/CF₃I 1-96/1-96 1-60HFC-1225ye/HFC-32/HFC- 1-97/1-97/1-97/ 10-80/5-70/5-70/5-70 125/HFC-152a1-97 HFC-1225ye/HFC-32/HFC- 1-97/1-97/1-97/ 5-70/5-70/5-70/1-30125/isobutane 1-97 HFC-1225ye/HFC-32/HFC- 1-97/1-97/1-97/5-70/5-70/5-70/1-30 125/propane 1-50 HFC-1225ye/HFC-32/HFC-1-97/1-97/1-97/ 5-70/5-70/5-70/1-30 125/DME 1-50HFC-1225ye/HFC-32/CF₃I/DME 1-97/1-97/1-97/ 5-70/5-70/5-70/1-30 1-50HFC-1225ye/HFC-32/HFC- 1-97/1-97/1-97/ 10-80/5-70/5-70/1-80 125/CF₃I1-97 HFC-1234yf/HFC-32/CF₃I 1-98/1-98/1-98 10-80/1-70/1-80HFC-1234yf/HFC-32/HFC- 1-97/1-97/1-97/ 5-70/5-80/1-70/5-70 134a/CF₃I1-97 HFC-1234yf/HFC-32/HFC-125 1-98/1-98/1-98 10-80/5-80/10-80HFC-1234yf/HFC-32/HFC- 1-97/1-97/1-97/ 10-80/5-70/10-80/5-80 125/CF3I1-97

The most preferred compositions of the present invention listed in Table2 are generally expected to maintain the desired properties andfunctionality when the components are present in the concentrations aslisted +/−2 weight percent. The compositions containing CO₂ would beexpected to maintain the desired properties and functionality when theCO₂ was present at the listed concentration +/−0.2 weight percent.

The compositions of the present invention may be azeotropic ornear-azeotropic compositions. By azeotropic composition is meant aconstant-boiling mixture of two or more substances that behave as asingle substance. One way to characterize an azeotropic composition isthat the vapor produced by partial evaporation or distillation of theliquid has the same composition as the liquid from which it isevaporated or distilled, i.e., the mixture distills/refluxes withoutcompositional change. Constant-boiling compositions are characterized asazeotropic because they exhibit either a maximum or minimum boilingpoint, as compared with that of the non-azeotropic mixture of the samecompounds. An azeotropic composition will not fractionate within arefrigeration or air conditioning system during operation, which mayreduce efficiency of the system. Additionally, an azeotropic compositionwill not fractionate upon leakage from a refrigeration or airconditioning system. In the situation where one component of a mixtureis flammable, fractionation during leakage could lead to a flammablecomposition either within the system or outside of the system.

A near-azeotropic composition (also commonly referred to as an“azeotrope-like composition”) is a substantially constant boiling liquidadmixture of two or more substances that behaves essentially as a singlesubstance. One way to characterize a near-azeotropic composition is thatthe vapor produced by partial evaporation or distillation of the liquidhas substantially the same composition as the liquid from which it wasevaporated or distilled, that is, the admixture distills/refluxeswithout substantial composition change. Another way to characterize anear-azeotropic composition is that the bubble point vapor pressure andthe dew point vapor pressure of the composition at a particulartemperature are substantially the same. Herein, a composition isnear-azeotropic if, after 50 weight percent of the composition isremoved, such as by evaporation or boiling off, the difference in vaporpressure between the original composition and the composition remainingafter 50 weight percent of the original composition has been removed isless than about 10 percent.

Azeotropic compositions of the present invention at a specifiedtemperature are shown in Table 3.

TABLE 3 Component A Component B Wt % A Wt % B Psia kPa T (C.) HFC-1234yfHFC-32 7.4 92.6 49.2 339 −25 HFC-1234yf HFC-125 10.9 89.1 40.7 281 −25HFC-1234yf HFC-134a 70.4 29.6 18.4 127 −25 HFC-1234yf HFC-152a 91.0 9.017.9 123 −25 HFC-1234yf HFC-143a 17.3 82.7 39.5 272 −25 HFC-1234yfHFC-227ea 84.6 15.4 18.0 124 −25 HFC-1234yf propane 51.5 48.5 33.5 231−25 HFC-1234yf n-butane 98.1 1.9 17.9 123 −25 HFC-1234yf isobutane 88.111.9 19.0 131 −25 HFC-1234yf DME 53.5 46.5 13.1 90 −25 HFC-1225yetrans-HFC-1234ze 63.0 37.0 11.7 81 −25 HFC-1225ye HFC-1243zf 40.0 60.013.6 94 −25 HFC-1225ye HFC-134 52.2 47.8 12.8 88 −25 HFC-1225ye HFC-152a7.3 92.7 14.5 100 −25 HFC-1225ye propane 29.7 70.3 30.3 209 −25HFC-1225ye n-butane 89.5 10.5 12.3 85 −25 HFC-1225ye isobutane 79.3 20.713.9 96 −25 HFC-1225ye DME 82.1 17.9 10.8 74 −25 HFC-1225ye CF₃SCF₃ 37.063.0 12.4 85 −25 trans-HFC-1234ze HFC-1243zf 17.0 83.0 13.0 90 −25trans-HFC-1234ze HFC-134 45.7 54.3 12.5 86 −25 trans-HFC-1234ze HFC-134a9.5 90.5 15.5 107 −25 trans-HFC-1234ze HFC-152a 21.6 78.4 14.6 101 −25trans-HFC-1234ze HFC-227ea 59.2 40.8 11.7 81 −25 trans-HFC-1234zepropane 28.5 71.5 30.3 209 −25 trans-HFC-1234ze n-butane 88.6 11.4 11.982 −25 trans-HFC-1234ze isobutane 77.9 22.1 12.9 89 −25 trans-HFC-1234zeDME 84.1 15.9 10.8 74 −25 trans-HFC-1234ze CF₃SCF₃ 34.3 65.7 12.7 88 −25HFC-1243zf HFC-134 63.0 37.0 13.5 93 −25 HFC-1243zf HFC-134A 25.1 74.915.9 110 −25 HFC-1243zf HFC-152A 40.7 59.3 15.2 104 −25 HFC-1243zfHFC-227ea 78.5 21.5 13.1 90 −25 HFC-1243zf propane 32.8 67.2 31.0 213−25 HFC-1243zf n-butane 90.3 9.7 13.5 93 −25 HFC-1243zf isobutane 80.719.3 14.3 98 −25 HFC-1243zf DME 72.7 27.3 12.0 83 −25 cis-HFC-1234zeHFC-236ea 20.9 79.1 30.3 209 25 cis-HFC-1234ze HFC-245fa 76.2 23.8 26.1180 25 cis-HFC-1234ze n-butane 51.4 48.6 6.08 42 −25 cis-HFC-1234zeisobutane 26.2 73.8 8.74 60 −25 cis-HFC-1234ze 2-methylbutane 86.6 13.427.2 188 25 cis-HFC-1234ze n-pentane 92.9 7.1 26.2 181 25 HFC-1234yeHFC-236ea 24.0 76.0 3.35 23.1 −25 HFC-1234ye HFC-245fa 42.5 57.5 22.8157 25 HFC-1234ye n-butane 41.2 58.8 38.0 262 25 HFC-1234ye isobutane16.4 83.6 50.9 351 25 HFC-1234ye 2-methylbutane 80.3 19.7 23.1 159 25HFC-1234ye n-pentane 87.7 12.3 21.8 150 25

Additionally, ternary azeotropes composition have been found as listedin Table 4.

TABLE 4 Pres Pres Temp Component A Component B Component C Wt % A Wt % BWt % C (psi) (kPa) (° C.) HFC-1234yf HFC-32 HFC-143A 3.9 74.3 21.8 50.02345 −25 HFC-1234yf HFC-32 isobutane 1.1 92.1 6.8 50.05 345 −25HFC-1234yf HFC-125 HFC-143A 14.4 43.5 42.1 38.62 266 −25 HFC-1234yfHFC-125 isobutane 9.7 89.1 1.2 40.81 281 −25 HFC-1234yf HFC-134 propane4.3 39.1 56.7 34.30 236 −25 HFC-1234yf HFC-134 DME 15.2 67.0 17.8 10.3871.6 −25 HFC-1234yf HFC-134a propane 24.5 31.1 44.5 34.01 234 −25HFC-1234yf HFC-134a n-butane 60.3 35.2 4.5 18.58 128 −25 HFC-1234yfHFC-134a isobutane 48.6 37.2 14.3 19.86 137 −25 HFC-1234yf HFC-134a DME24.0 67.9 8.1 17.21 119 −25 HFC-1234yf HFC-143a propane 17.7 71.0 11.340.42 279 −25 HFC-1234yf HFC-143a DME 5.7 93.0 1.3 39.08 269 −25HFC-1234yf HFC-152a n-butane 86.6 10.8 2.7 17.97 124 −25 HFC-1234yfHFC-152a isobutane 75.3 11.8 12.9 19.12 132 −25 HFC-1234yf HFC-152a DME24.6 43.3 32.1 11.78 81.2 −25 HFC-1234yf HFC-227ea propane 35.6 17.846.7 33.84 233 −25 HFC-1234yf HFC-227ea n-butane 81.9 16.0 2.1 18.07 125−25 HFC-1234yf HFC-227ea isobutane 70.2 18.2 11.6 19.27 133 −25HFC-1234yf HFC-227ea DME 28.3 55.6 16.1 15.02 104 −25 HFC-1234yfn-butane DME 48.9 4.6 46.4 13.15 90.7 −25 HFC-1234yf isobutane DME 31.226.2 42.6 14.19 97.8 −25 HFC-1234yf DME CF₃I 16.3 10.0 73.7 15.65 108−25 HFC-1234yf DME CF₃SCF₃ 34.3 10.5 55.2 14.57 100 −25 HFC-1225yetrans-HFC- HFC-134 47.4 5.6 47.0 12.77 88.0 −25 1234ze HFC-1225yetrans-HFC- HFC-227ea 28.4 52.6 19.0 11.63 80.2 −25 1234ze HFC-1225yetrans-HFC- propane 20.9 9.1 70.0 30.36 209 −25 1234ze HFC-1225yetrans-HFC- n-butane 65.8 24.1 10.1 12.39 85.4 −25 1234ze HFC-1225yetrans-HFC- DME 41.0 40.1 18.9 10.98 75.7 −25 1234ze HFC-1225yetrans-HFC- CF₃SCF₃ 1.0 33.7 65.2 12.66 87.3 −25 1234ze HFC-1225yeHFC-1243zf HFC-134 28.7 47.3 24.1 13.80 95.1 −25 HFC-1225ye HFC-1243zfn-butane 37.5 55.0 7.5 13.95 96.2 −25 HFC-1225ye HFC-1243zf isobutane40.5 43.2 16.3 14.83 102 −25 HFC-1225ye HFC-1243zf DME 19.1 51.0 29.912.15 83.8 −25 HFC-1225ye HFC-1243zf CF₃I 10.3 27.3 62.3 14.05 96.9 −25HFC-1225ye HFC-134 HFC-152a 63.6 26.8 9.6 12.38 85.4 −25 HFC-1225yeHFC-134 HFC-227ea 1.3 52.3 46.4 12.32 84.9 −25 HFC-1225ye HFC-134n-butane 18.1 67.1 14.9 14.54 100 −25 HFC-1225ye HFC-134 isobutane 0.774.0 25.3 16.68 115 −25 HFC-1225ye HFC-134 DME 29.8 52.5 17.8 9.78 67.4−25 HFC-1225ye HFC-227ea DME 63.1 31.0 5.8 10.93 75.4 −25 HFC-1225yen-butane DME 66.0 13.0 21.1 11.34 78.2 −25 HFC-1225ye n-butane CF₃SCF₃71.3 5.6 23.0 12.25 84.5 −25 HFC-1225ye isobutane DME 49.9 29.7 20.412.83 88.5 −25 HFC-1225ye isobutane CF₃I 27.7 2.2 70.1 13.19 90.9 −25trans-HFC- HFC-1243zf HFC-227ea 7.1 73.7 19.2 13.11 90.4 −25 1234zetrans-HFC- HFC-1243zf n-butane 9.5 81.2 9.3 13.48 92.9 −25 1234zetrans-HFC- HFC-1243zf isobutane 3.3 77.6 19.1 14.26 98.3 −25 1234zetrans-HFC- HFC-1243zf DME 2.6 70.0 27.4 12.03 82.9 −25 1234ze trans-HFC-HFC-134 HFC-152a 52.0 42.9 5.1 12.37 85.3 −25 1234ze trans-HFC- HFC-134HFC-227ea 30.0 43.2 26.8 12.61 86.9 −25 1234ze trans-HFC- HFC-134 DME27.7 54.7 17.7 9.76 67.3 −25 1234ze trans-HFC- HFC-134a HFC-152a 14.434.7 51.0 14.42 99.4 −25 1234ze trans-HFC- HFC-152a n-butane 5.4 80.514.1 15.41 106 −25 1234ze trans-HFC- HFC-152a DME 59.1 16.4 24.5 10.8074.5 −25 1234ze trans-HFC- HFC-227ea n-butane 40.1 48.5 11.3 12.61 86.9−25 1234ze trans-HFC- n-butane DME 68.1 13.0 18.9 11.29 77.8 −25 1234zetrans-HFC- n-butane CF₃I 81.2 9.7 9.1 11.87 81.8 −25 1234ze trans-HFC-isobutane DME 55.5 28.7 15.8 12.38 85.4 −25 1234ze trans-HFC- isobutaneCF₃I 34.9 6.1 59.0 12.57 86.7 −25 1234ze trans-HFC- isobutane CF₃SCF₃37.7 1.1 61.7 12.66 87.3 −25 1234ze HFC-1243zf HFC-134 HFC-227ea 58.634.1 7.3 13.54 93.4 −25 HFC-1243zf HFC-134 n-butane 27.5 58.7 13.9 14.72101 −25 HFC-1243zf HFC-134 DME 18.7 63.5 17.8 10.11 69.7 −25 HFC-1243zfHFC-134 CF₃I 11.4 23.9 64.7 14.45 99.6 −25 HFC-1243zf HFC-134a HFC-152a41.5 21.5 37.1 14.95 103 −25 HFC-1243zf HFC-134A n-butane 7.0 81.4 11.617.03 117 −25 HFC-1243zf HFC-152a propane 2.9 34.0 63.0 31.73 219 −25HFC-1243zf HFC-152a n-butane 28.8 60.3 11.0 15.71 108 −25 HFC-1243zfHFC-152a isobutane 6.2 68.5 25.3 17.05 118 −25 HFC-1243zf HFC-152a DME33.1 36.8 30.1 11.41 78.7 −25 HFC-1243zf HFC-227ea n-butane 62.0 28.49.6 13.67 94.3 −25 HFC-1243zf HFC-227ea isobutane 27.9 51.0 21.1 15.00103 −25 HFC-1243zf HFC-227ea DME 48.1 44.8 7.2 12.78 88.1 −25 HFC-1243zfn-butane DME 60.3 10.1 29.6 12.28 84.7 −25 HFC-1243zf isobutane DME 47.126.9 25.9 13.16 90.7 −25 HFC-1243zf isobutane CF₃I 32.8 1.1 66.1 13.9796.3 −25 HFC-1243zf DME CF₃SCF₃ 41.1 2.3 56.6 13.60 93.8 −25

The near-azeotropic compositions of the present invention at a specifiedtemperature are listed in Table 5.

TABLE 5 Component A Component B (wt % A/wt % B) T (C.) HFC-1234yf HFC-321-57/99-43 −25 HFC-1234yf HFC-125 1-51/99-49 −25 HFC-1234yf HFC-1341-99/99-1 −25 HFC-1234yf HFC-134a 1-99/99-1 −25 HFC-1234yf HFC-152a1-99/99-1 −25 HFC-1234yf HFC-161 1-99/99-1 −25 HFC-1234yf HFC-143a1-60/99-40 −25 HFC-1234yf HFC-227ea 29-99/71-1 −25 HFC-1234yf HFC-236fa66-99/34-1 −25 HFC-1234yf HFC-1225ye 1-99/99-1 −25 HFC-1234yftrans-HFC-1234ze 1-99/99-1 −25 HFC-1234yf HFC-1243zf 1-99/99-1 −25HFC-1234yf propane 1-80/99-20 −25 HFC-1234yf n-butane 71-99/29-1 −25HFC-1234yf isobutane 60-99/40-1 −25 HFC-1234yf DME 1-99/99-1 −25HFC-1225ye trans-HFC-1234ze 1-99/99-1 −25 HFC-1225ye HFC-1243zf1-99/99-1 −25 HFC-1225ye HFC-134 1-99/99-1 −25 HFC-1225ye HFC-134a1-99/99-1 −25 HFC-1225ye HFC-152a 1-99/99-1 −25 HFC-1225ye HFC-1611-84/99-16, 90-99/ −25 10-1 HFC-1225ye HFC-227ea 1-99/99-1 −25HFC-1225ye HFC-236ea 57-99/43-1 −25 HFC-1225ye HFC-236fa 48-99/52-1 −25HFC-1225ye HFC-245fa 70-99/30-1 −25 HFC-1225ye propane 1-72/99-28 −25HFC-1225ye n-butane 65-99/35-1 −25 HFC-1225ye isobutane 50-99/50-1 −25HFC-1225ye DME 1-99/99-1 −25 HFC-1225ye CF₃I 1-99/99-1 −25 HFC-1225yeCF₃SCF₃ 1-99/99-1 −25 trans-HFC-1234ze cis-HFC-1234ze 73-99/27-1 −25trans-HFC-1234ze HFC-1243zf 1-99/99-1 −25 trans-HFC-1234ze HFC-1341-99/99-1 −25 trans-HFC-1234ze HFC-134a 1-99/99-1 −25 trans-HFC-1234zeHFC-152a 1-99/99-1 −25 trans-HFC-1234ze HFC-161 1-52/99-48, 87-99/ −2513-1 trans-HFC-1234ze HFC-227ea 1-99/99-1 −25 trans-HFC-1234ze HFC-236ea54-99/46-1 −25 trans-HFC-1234ze HFC-236fa 44-99/56-1 −25trans-HFC-1234ze HFC-245fa 67-99/33-1 −25 trans-HFC-1234ze propane1-71/99-29 −25 trans-HFC-1234ze n-butane 62-99/38-1 −25 trans-HFC-1234zeisobutane 39-99/61-1 −25 trans-HFC-1234ze DME 1-99/99-1 −25trans-HFC-1234ze CF₃SCF₃ 1-99/99-1 −25 trans-HFC-1234ze CF₃I 1-99/99-1−25 HFC-1243zf HFC-134 1-99/99-1 −25 HFC-1243zf HFC-134a 1-99/99-1 −25HFC-1243zf HFC-152a 1-99/99-1 −25 HFC-1243zf HFC-161 1-99/99-1 −25HFC-1243zf HFC-227ea 1-99/99-1 −25 HFC-1243zf HFC-236ea 53-99/47-1 −25HFC-1243zf HFC-236fa 49-99/51-1 −25 HFC-1243zf HFC-245fa 66-99/34-1 −25HFC-1243zf propane 1-71/99-29 −25 HFC-1243zf n-butane 62-99/38-1 −25HFC-1243zf isobutane 45-99/55-1 −25 HFC-1243zf DME 1-99/99-1 −25cis-HFC-1234ze HFC-236ea 1-99/99-1 25 cis-HFC-1234ze HFC-236fa 1-99/99-125 cis-HFC-1234ze HFC-245fa 1-99/99-1 25 cis-HFC-1234ze n-butane1-80/99-20 −25 cis-HFC-1234ze isobutane 1-69/99-31 −25 cis-HFC-1234ze2-methylbutane 60-99/40-1 25 cis-HFC-1234ze n-pentane 63-99/37-1 25HFC-1234ye HFC-134 38-99/62-1 25 HFC-1234ye HFC-236ea 1-99/99-1 −25HFC-1234ye HFC-236fa 1-99/99-1 25 HFC-1234ye HFC-245fa 1-99/99-1 25HFC-1234ye Cis-HFC-1234ze 1-99/99-1 25 HFC-1234ye n-butane 1-78/99-22 25HFC-1234ye cyclopentane 70-99/30-1 25 HFC-1234ye isobutane 1-68/99-32 25HFC-1234ye 2-methylbutane 47-99/53-1 25 HFC-1234ye n-pentane 57-99/43-125

Ternary and higher order near-azeotrope compositions comprisingfluoroolefin have also been identified as listed in Table 6.

TABLE 6 Near-azeotrope range Temp Components (weight percent) (° C.)HFC-1225ye/HFC-134a/HFC-152a 1-98/1-98/1-98 25HFC-1225ye/HFC-134a/HFC-161 1-98/1-98/1-98 25HFC-1225ye/HFC-134a/isobutane 1-98/1-98/1-40 25 HFC-1225ye/HFC-134a/DME1-98/1-98/1-20 25 HFC-1225ye/HFC-152a/isobutane 1-98/1-98/1-50 25HFC-1225ye/HFC-152a/DME 1-98/1-98/1-98 25 HFC-1225ye/HFC-1234yf/HFC-134a1-98/1-98/1-98 25 HFC-1225ye/HFC-1234yf/HFC-152a 1-98/1-98/1-98 25HFC-1225ye/HFC-1234yf/HFC-125 1-98/1-98/1-20 25HFC-1225ye/HFC-1234yf/CF₃I 1-98/1-98/1-98 25 HFC-1225ye/HFC-134a/HFC-1-97/1-97/1-97/1-10 25 152a/HFC-32 HFC-125/HFC-1225ye/isobutane80-98/1-19/1-10 25 HFC-125/trans-HFC- 80-98/1-19/1-10 251234ze/isobutane HFC-125/HFC-1234yf/isobutane 80-98/1-19/1-10 25HFC-32/HFC-125/HFC-1225ye 1-98/1-98/1-4 25HFC-32/HFC-125/trans-HFC-1234ze 1-98/1-98/1-50 25HFC-32/HFC-125/HFC-1234yf 1-98/1-98/1-55 25HFC-125/trans-HFC-1234ze/n-butane 80-98/1-19/1-10 25HFC-125/HFC-1234yf/n-butane 80-98/1-19/1-10 25HFC-1234yf/HFC-32/HFC-143a 1-50/1-98/1-98 −25HFC-1234yf/HFC-32/isobutane 1-40/59-98/1-30 −25HFC-1234yf/HFC-125/HFC-143a 1-60/1-98/1-98 −25HFC-1234yf/HFC-125/isobutane 1-40/59-98/1-20 −25HFC-1234yf/HFC-134/propane 1-80/1-70/19-90 −25 HFC-1234yf/HFC-134/DME1-70/1-98/29-98 −25 HFC-1234yf/HFC-134a/propane 1-80/1-80/19-98 −25HFC-1234yf/HFC-134a/n-butane 1-98/1-98/1-30 −25HFC-1234yf/HFC-134a/isobutane 1-98/1-98/1-30 −25 HFC-1234yf/HFC-134a/DME1-98/1-98/1-40 −25 HFC-1234yf/HFC-143a/propane 1-80/1-98/1-98 −25HFC-1234yf/HFC-143a/DME 1-40/59-98/1-20 −25 HFC-1234yf/HFC-152a/n-butane1-98/1-98/1-30 −25 HFC-1234yf/HFC-152a/isobutane 1-98/1-90/1-40 −25HFC-1234yf/HFC-152a/DME 1-70/1-98/1-98 −25 HFC-1234yf/HFC-227ea/propane1-80/1-70/29-98 −25 HFC-1234yf/HFC-227ea/n-butane 40-98/1-59/1-20 −25HFC-1234yf/HFC-227ea/isobutane 30-98/1-69/1-30 −25HFC-1234yf/HFC-227ea/DME 1-98/1-80/1-98 −25 HFC-1234yf/n-butane/DME1-98/1-40/1-98 −25 HFC-1234yf/isobutane/DME 1-98/1-50/1-98 −25HFC-1234yf/DME/CF₃I 1-98/1-98/1-98 −25 HFC-1234yf/DME/CF₃SCF₃1-98/1-40/1-80 −25 HFC-1225ye/trans-HFC- 1-98/1-98/1-98 −251234ze/HFC-134 HFC-1225ye/trans-HFC- 1-98/1-98/1-98 −25 1234ze/HFC-227eaHFC-1225ye/trans-HFC- 1-60/1-60/1-98 −25 1234ze/propaneHFC-1225ye/trans-HFC-1234ze/n- 1-98/1-98/1-30 −25 butaneHFC-1225ye/trans-HFC-1234ze/DME 1-98/1-98/1-98 −25HFC-1225ye/trans-HFC-1234ze/ 1-98/1-98/1-98 −25 CF₃SCF₃HFC-1225ye/HFC-1243zf/HFC-134 1-98/1-98/1-98 −25HFC-1225ye/HFC-1243zf/n-butane 1-98/1-98/1-30 −25HFC-1225ye/HFC-1243zf/isobutane 1-98/1-98/1-40 −25HFC-1225ye/HFC-1243zf/DME 1-98/1-98/1-98 −25 HFC-1225ye/HFC-1243zf/CF₃I1-98/1-98/1-98 −25 HFC-1225ye/HFC-134/HFC-152a 1-98/1-98/1-98 −25HFC-1225ye/HFC-134/HFC-227ea 1-98/1-98/1-98 −25HFC-1225ye/HFC-134/n-butane 1-98/1-90/1-40 −25HFC-1225ye/HFC-134/isobutane 1-98/1-90/1-40 −25 HFC-1225ye/HFC-134/DME1-98/1-98/1-40 −25 HFC-1225ye/HFC-227ea/DME 40-98/1-59/1-30 −25HFC-1225ye/n-butane/DME 1-98/1-30/1-98 −25 HFC-1225ye/n-butane/CF₃SCF₃1-98/1-20/1-98 −25 HFC-1225ye/isobutane/DME 1-98/1-60/1-98 −25HFC-1225ye/isobutane/CF₃I 1-98/1-40/1-98 −25trans-HFC-1234ze/HFC-1243zf/HFC- 1-98/1-98/1-98 −25 227eatrans-HFC-1234ze/HFC-1243zf/n- 1-98/1-98/1-30 −25 butanetrans-HFC-1234ze/HFC- 1-98/1-98/1-40 −25 1243zf/isobutanetrans-HFC-1234ze/HFC-1243zf/DME 1-98/1-98/1-98 −25trans-HFC-1234ze/HFC-134/HFC- 1-98/1-98/1-98 −25 152atrans-HFC-1234ze/HFC-134/HFC- 1-98/1-98/1-98 −25 227eatrans-HFC-1234ze/HFC-134/DME 1-98/1-98/1-40 −25trans-HFC-1234ze/HFC-134a/HFC- 1-98/1-98/1-98 −25 152atrans-HFC-1234ze/HFC-152a/n- 1-98/1-98/1-50 −25 butanetrans-HFC-1234ze/HFC-152a/DME 1-98/1-98/1-98 −25trans-HFC-1234ze/HFC-227ea/n- 1-98/1-98/1-40 −25 butanetrans-HFC-1234ze/n-butane/DME 1-98/1-40/1-98 −25trans-HFC-1234ze/n-butane/CF₃I 1-98/1-30/1-98 −25trans-HFC-1234ze/isobutane/DME 1-98/1-60/1-98 −25trans-HFC-1234ze/isobutane/CF₃I 1-98/1-40/1-98 −25trans-HFC-1234ze/isobutane/ 1-98/1-40/1-98 −25 CF₃SCF₃HFC-1243zf/HFC-134/HFC-227ea 1-98/1-98/1-98 −25HFC-1243zf/HFC-134/n-butane 1-98/1-98/1-40 −25 HFC-1243zf/HFC-134/DME1-98/1-98/1-98 −25 HFC-1243zf/HFC-134/CF₃I 1-98/1-98/1-98 −25HFC-1243zf/HFC-134a/HFC-152a 1-98/1-98/1-98 −25HFC-1243zf/HFC-134a/n-butane 1-98/1-98/1-40 −25HFC-1243zf/HFC-152a/propane 1-70/1-70/29-98 −25HFC-1243zf/HFC-152a/n-butane 1-98/1-98/1-30 −25HFC-1243zf/HFC-152a/isobutane 1-98/1-98/1-40 −25 HFC-1243zf/HFC-152a/DME1-98/1-98/1-98 −25 HFC-1243zf/HFC-227ea/n-butane 1-98/1-98/1-40 −25HFC-1243zf/HFC-227ea/isobutane 1-98/1-90/1-50 −25HFC-1243zf/HFC-227ea/DME 1-98/1-80/1-90 −25 HFC-1243zf/n-butane/DME1-98/1-40/1-98 −25 HFC-1243zf/isobutane/DME 1-98/1-60/1-98 −25HFC-1243zf/isobutane/CF₃I 1-98/1-40/1-98 −25 HFC-1243zf/DME/CF₃SCF₃1-98/1-40/1-90 −25

Certain of the compositions of the present invention are non-azeotropiccompositions. Those compositions of the present invention falling withinthe preferred ranges of Table 2, but outside of the near-azeotropicranges of Table 5 and Table 6 may be considered to be non-azeotropic.

A non-azeotropic composition may have certain advantages over azeotropicor near azeotropic mixtures. A non-azeotropic composition is a mixtureof two or more substances that behaves as a mixture rather than a singlesubstance. One way to characterize a non-azeotropic composition is thatthe vapor produced by partial evaporation or distillation of the liquidhas a substantially different composition as the liquid from which itwas evaporated or distilled, that is, the admixture distills/refluxeswith substantial composition change. Another way to characterize anon-azeotropic composition is that the bubble point vapor pressure andthe dew point vapor pressure of the composition at a particulartemperature are substantially different. Herein, a composition isnon-azeotropic if, after 50 weight percent of the composition isremoved, such as by evaporation or boiling off, the difference in vaporpressure between the original composition and the composition remainingafter 50 weight percent of the original composition has been removed isgreater than about 10 percent.

The compositions of the present invention may be prepared by anyconvenient method to combine the desired amounts of the individualcomponents. A preferred method is to weigh the desired component amountsand thereafter combine the components in an appropriate vessel.Agitation may be used, if desired.

An alternative means for making compositions of the present inventionmay be a method for making a refrigerant blend composition, wherein saidrefrigerant blend composition comprises a composition as disclosedherein, said method comprising (i) reclaiming a volume of one or morecomponents of a refrigerant composition from at least one refrigerantcontainer, (ii) removing impurities sufficiently to enable reuse of saidone or more of the reclaimed components, (iii) and optionally, combiningall or part of said reclaimed volume of components with at least oneadditional refrigerant composition or component.

A refrigerant container may be any container in which is stored arefrigerant blend composition that has been used in a refrigerationapparatus, air-conditioning apparatus or heat pump apparatus. Saidrefrigerant container may be the refrigeration apparatus,air-conditioning apparatus or heat pump apparatus in which therefrigerant blend was used. Additionally, the refrigerant container maybe a storage container for collecting reclaimed refrigerant blendcomponents, including but not limited to pressurized gas cylinders.

Residual refrigerant means any amount of refrigerant blend orrefrigerant blend component that may be moved out of the refrigerantcontainer by any method known for transferring refrigerant blends orrefrigerant blend components.

Impurities may be any component that is in the refrigerant blend orrefrigerant blend component due to its use in a refrigeration apparatus,air-conditioning apparatus or heat pump apparatus. Such impuritiesinclude but are not limited to refrigeration lubricants, being thosedescribed earlier herein, particulates including but not limited tometal, metal salt or elastomer particles, that may have come out of therefrigeration apparatus, air-conditioning apparatus or heat pumpapparatus, and any other contaminants that may adversely effect theperformance of the refrigerant blend composition.

Such impurities may be removed sufficiently to allow reuse of therefrigerant blend or refrigerant blend component without adverselyeffecting the performance or equipment within which the refrigerantblend or refrigerant blend component will be used.

It may be necessary to provide additional refrigerant blend orrefrigerant blend component to the residual refrigerant blend orrefrigerant blend component in order to produce a composition that meetsthe specifications required for a given product. For instance, if arefrigerant blend has 3 components in a particular weight percentagerange, it may be necessary to add one or more of the components in agiven amount in order to restore the composition to within thespecification limits.

Compositions of the present invention have zero or low ozone depletionpotential and low global warming potential (GWP). Additionally, thecompositions of the present invention will have global warmingpotentials that are less than many hydrofluorocarbon refrigerantscurrently in use. One aspect of the present invention is to provide arefrigerant with a global warming potential of less than 1000, less than500, less than 150, less than 100, or less than 50. Another aspect ofthe present invention is to reduce the net GWP of refrigerant mixturesby adding fluoroolefins to said mixtures.

The compositions of the present invention may be useful as low globalwarming potential (GWP) replacements for currently used refrigerants,including but not limited to R134a (or HFC-134a,1,1,1,2-tetrafluoroethane), R22 (or HCFC-22, chlorodifluoromethane),R123 (or HFC-123,2,2-dichloro-1,1,1-trifluoroethane), R11 (CFC-11,fluorotrichloromethane), R12 (CFC-12, dichlorodifluoromethane), R245fa(or HFC-245fa, 1,1,1,3,3-pentafluoropropane), R114 (orCFC-114,1,2-dichloro-1,1,2,2-tetrafluoroethane), R236fa (or HFC-236fa,1,1,1,3,3,3-hexafluoropropane), R124 (or HCFC-124,2-chloro-1,1,1,2-tetrafluoroethane), R407C (ASHRAE designation for ablend of 52 weight percent R134a, 25 weight percent R125(pentafluoroethane), and 23 weight percent R32 (difluoromethane), R410A(ASHRAE designation for a blend of 50 weight percent R125 and 50 weightpercent R32), R417A, (ASHRAE designation for a blend of 46.6 weightpercent R125, 50.0 weight percent R134a, and 3.4 weight percentn-butane), R422A, R422B, R422C and R422D, (ASHRAE designation for ablend of 85.1 weight percent R125, 11.5 weight percent R134a, and 3.4weight percent isobutane), R404A, (ASHRAE designation for a blend of 44weight percent R125, 52 weight percent R143a (1,1,1-trifluoroethane),and 4.0 weight percent R134a) and R507A (ASHRAE designation for a blendof 50 weight percent R125 and 50 weight percent R143a). Additionally,the compositions of the present invention may be useful as replacementsfor R12 (CFC-12, dichlorodifluoromethane) or R502 (ASHRAE designationfor a blend of 51.2 weight percent CFC-115 (chloropentafluoroethane) and48.8 weight percent HCFC-22).

Often replacement refrigerants are most useful if capable of being usedin the original refrigeration equipment designed for a differentrefrigerant. The compositions of the present invention may be useful asreplacements for the above-mentioned refrigerants in original equipment.Additionally, the compositions of the present invention may be useful asreplacements for the above mentioned refrigerants in equipment designedto use the above-mentioned refrigerants.

The compositions of the present invention may further comprise alubricant. Lubricants of the present invention comprise refrigerationlubricants, i.e. those lubricants suitable for use with refrigeration,air-conditioning, or heat pump apparatus. Among these lubricants arethose conventionally used in compression refrigeration apparatusutilizing chlorofluorocarbon refrigerants. Such lubricants and theirproperties are discussed in the 1990 ASHRAE Handbook, RefrigerationSystems and Applications, chapter 8, titled “Lubricants in RefrigerationSystems”, pages 8.1 through 8.21. Lubricants of the present inventionmay comprise those commonly known as “mineral oils” in the field ofcompression refrigeration lubrication. Mineral oils comprise paraffins(i.e. straight-chain and branched-carbon-chain, saturated hydrocarbons),naphthenes (i.e. cyclic paraffins) and aromatics (i.e. unsaturated,cyclic hydrocarbons containing one or more rings characterized byalternating double bonds). Lubricants of the present invention furthercomprise those commonly known as “synthetic oils” in the field ofcompression refrigeration lubrication. Synthetic oils comprisealkylaryls (i.e. linear and branched alkyl alkylbenzenes), syntheticparaffins and napthenes, and poly(alphaolefins). Representativeconventional lubricants of the present invention are the commerciallyavailable BVM 100 N (paraffinic mineral oil sold by BVA Oils), Suniso®3GS and Suniso® 5GS (naphthenic mineral oil sold by Crompton Co.),Sontex® 372LT (naphthenic mineral oil sold by Pennzoil), Calumet® RO-30(naphthenic mineral oil sold by Calumet Lubricants), Zerol® 75, Zerol®150 and Zerol® 500 (linear alkylbenzenes sold by Shrieve Chemicals) andHAB 22 (branched alkylbenzene sold by Nippon Oil).

Lubricants of the present invention further comprise those that havebeen designed for use with hydrofluorocarbon refrigerants and aremiscible with refrigerants of the present invention under compressionrefrigeration, air-conditioning, or heat pump apparatus' operatingconditions. Such lubricants and their properties are discussed in“Synthetic Lubricants and High-Performance Fluids”, R. L. Shubkin,editor, Marcel Dekker, 1993. Such lubricants include, but are notlimited to, polyol esters (POEs) such as Castrol® 100 (Castrol, UnitedKingdom), polyalkylene glycols (PAGs) such as RL-488A from Dow (DowChemical, Midland, Mich.), and polyvinyl ethers (PVEs). These lubricantsare readily available from various commercial sources.

Lubricants of the present invention are selected by considering a givencompressor's requirements and the environment to which the lubricantwill be exposed. Lubricants of the present invention preferably have akinematic viscosity of at least about 5 cs (centistokes) at 40° C.

Commonly used refrigeration system additives may optionally be added, asdesired, to compositions of the present invention in order to enhancelubricity and system stability. These additives are generally knownwithin the field of refrigeration compressor lubrication, and includeanti wear agents, extreme pressure lubricants, corrosion and oxidationinhibitors, metal surface deactivators, free radical scavengers, foamingand antifoam control agents, leak detectants and the like. In general,these additives are present only in small amounts relative to theoverall lubricant composition. They are typically used at concentrationsof from less than about 0.1% to as much as about 3% of each additive.These additives are selected on the basis of the individual systemrequirements. Some typical examples of such additives may include, butare not limited to, lubrication enhancing additives, such as alkyl oraryl esters of phosphoric acid and of thiophosphates. Additionally, themetal dialkyl dithiophosphates (e.g. zinc dialkyl dithiophosphate orZDDP, Lubrizol 1375) and other members of this family of chemicals maybe used in compositions of the present invention. Other antiwearadditives include natural product oils and assymetrical polyhydroxyllubrication additives such as Synergol TMS (International Lubricants).Similarly, stabilizers such as anti oxidants, free radical scavengers,and water scavengers may be employed. Compounds in this category caninclude, but are not limited to, butylated hydroxy toluene (BHT) andepoxides.

The compositions of the present invention may further comprise about0.01 weight percent to about 5 weight percent of an additive such as,for example, a stabilizer, free radical scavenger and/or antioxidant.Such additives include but are not limited to, nitromethane, hinderedphenols, hydroxylamines, thiols, phosphites, or lactones. Singleadditives or combinations may be used.

The compositions of the present invention may further comprise about0.01 weight percent to about 5 weight percent of a water scavenger(drying compound). Such water scavengers may comprise ortho esters suchas trimethyl-, triethyl-, or tripropylortho formate.

The compositions of the present invention may further comprise a tracerselected from the group consisting of hydrofluorocarbons (HFCs),deuterated hydrocarbons, deuterated hydrofluorocarbons,perfluorocarbons, fluoroethers, brominated compounds, iodated compounds,alcohols, aldehydes, ketones, nitrous oxide (N₂O) and combinationsthereof. The tracer compounds are added to the compositions inpreviously determined quantities to allow detection of any dilution,contamination or other alteration of the composition, as described inU.S. patent application Ser. No. 11/062,044, filed Feb. 18, 2005.

Typical tracer compounds for use in the present compositions are listedin Table 7.

TABLE 7 Compound Structure Deuterated hydrocarbons andhydrofluorocarbons Ethane-d6 CD₃CD₃ Propane-d8 CD₃CD₂CD₃ HFC-32-d2 CD₂F₂HFC-134a-d2 CD₂FCF₃ HFC-143a-d3 CD₃CF₃ HFC-125-d CDF₂CF₃ HFC-227ea-dCF₃CDFCF₃ HFC-227ca-d CF₃CF₂CDF₂ HFC-134-d2 CDF₂CDF₂ HFC-236fa-d2CF₃CD₂CF₃ HFC-245cb-d3 CF₃CF₂CD₃ HFC-263fb-d2* CF₃CD₂CH₃ HFC-263fb-d3CF₂CH₂CD₃ Fluoroethers HFOC-125E CHF₂OCF₃ HFOC-134aE CH₂FOCF₃ HFOC-143aECH₃OCF₃ HFOC-227eaE CF₃OCHFCF₃ HFOC-236faE CF₃OCH₂CF₃ HFOC-245faEβγ orCHF₂OCH₂CF₃ HFOC-245faEαβ (or CHF₂CH₂OCF₃) HFOC-245cbEβγ or CH₃OCF₂CF₃HFOC-245cbαβ (or CH₃CF₂OCF₃) HFE-42-11mcc (or Freon ® E1)CF₃CF₂CF₂OCHFCF₃ Freon ® E2 CF₃CF₂CF₂OCF(CF₃) CF₂OCHFCF₃Hydrofluorocarbons HFC-23 CHF₃ HFC-161 CH₃CH₂F HFC-152a CH₃CHF₂ HFC-134CHF₂CHF₂ HFC-227ea CF₃CHFCF₃ HFC-227ca CHF₂CF₂CF₃ HFC-236cb CH₂FCF₂CF₃HFC-236ea CF₃CHFCHF₂ HFC-236fa CF₃CH₂CF₃ HFC-245cb CF₃CF₂CH₃ HFC-245faCHF₂CH₂CF₃ HFC-254cb CHF₂CF₂CH₃ HFC-254eb CF₃CHFCH₃ HFC-263fb CF₃CH₂CH₃HFC-272ca CH₃CF₂CH₃ HFC-281ea CH₃CHFCH₃ HFC-281fa CH₂FCH₂CH₃ HFC-329pCHF₂CF₂CF₂CF₃ HFC-329mmz (CH₃)₂CHCF₃ HFC-338mf CF₃CH₂CF₂CF₃ HFC-338ppcCHF₂CF₂CF₂CHF₂ HFC-347s CH₃CF₂CF₂CF₃ HFC-43-10mee CF₃CHFCHFCF₂CF₃Perfluorocarbons PFC-116 CF₃CF₃ PFC-C216 Cyclo(—CF₂CF₂CF₂—) PFC-218CF₃CF₂CF₃ PFC-C318 Cyclo(—CF₂CF₂CF₂CF₂—) PFC-31-10mc CF₃CF₂CF₂CF₃PFC-31-10my (CF₃)₂CFCF₃ PFC-C51-12mycm Cyclo(—CF(CF₃)CF₂CF(CF₃)CF₂—)PFC-C51-12mym, trans-cyclo(—CF₂CF(CF₃)CF(CF₃)CF₂—) PFC-C51-12mym,cis-cyclo(—CF₂CF(CF₃)CF(CF₃)CF₂—) Perfluoromethylcyclo-pentaneCyclo(—CF₂CF₂(CF₃)CF₂CF₂CF₂—) Perfluoromethylcyclo-hexaneCyclo(—CF₂CF₂(CF₃)CF₂CF₂CF₂CF₂—) Perfluorodimethylcyclo-hexane (ortho,Cyclo(—CF₂CF₂(CF₃)CF₂CF₂(CF₃)CF₂—) meta, or para)Perfluoroethylcyclohexane Cyclo(—CF₂CF₂(CF₂CF₃)CF₂CF₂CF₂CF₂—)Perfluoroindan C₉F₁₀ (see structure below)

Perfluorotrimethylcyclo-hexane (allCyclo(—CF₂(CF₃)CF₂(CF₃)CF₂CF₂(CF₃)CF₂—) possible isomers)Perfluoroisopropylcyclo-hexane Cyclo(—CF₂CF₂(CF₂(CF₃)₂)CF₂CF₂CF₂CF₂—)Perfluorodecalin (cis or trans, trans shown) C₁₀F₁₈ (see structurebelow)

Perfluoromethyldecalin (cis or trans and all additional possibleisomers) C₁₁F₂₀ (see structure below)

Brominated compounds Bromomethane CH₃Br Bromofluoromethane CH₂FBrBromodifluoromethane CHF₂Br Dibromofluoromethane CHFBr₂ TribromomethaneCHBr₃ Bromoethane CH₃CH₂Br Bromoethene CH₂═CHBr 1,2-dibromoethaneCH₂BrCH₂Br 1-bromo-1,2-difluoroethene CFBr═CHF Iodated compoundsIodotrifluoromethane CF₃I Difluoroiodomethane CHF₂I FluoroiodomethaneCH₂FI 1,1,2-trifluoro-1-iodoethane CF₂ICH₂F1,1,2,2-tetrafluoro-1-iodoethane CF₂ICHF₂1,1,2,2-tetrafluoro-1,2-diiodoethane CF₂ICF₂I IodopentafluorobenzeneC₆F₅I Alcohols Ethanol CH₃CH₂OH n-propanol CH₃CH₂CH₂OH IsopropanolCH₃CH(OH)CH₃ Aldehydes and Ketones Acetone (2-propanone) CH₃C(O)CH₃n-propanal CH₃CH₂CHO n-butanal CH₃CH₂CH₂CHO Methyl ethyl ketone(2-butanone) CH₃C(O)CH₂CH₃ Other Nitrous oxide N₂O

The compounds listed in Table 7 are available commercially (fromchemical supply houses) or may be prepared by processes known in theart.

Single tracer compounds may be used in combination with arefrigeration/heating fluid in the compositions of the present inventionor multiple tracer compounds may be combined in any proportion to serveas a tracer blend. The tracer blend may contain multiple tracercompounds from the same class of compounds or multiple tracer compoundsfrom different classes of compounds. For example, a tracer blend maycontain 2 or more deuterated hydrofluorocarbons, or one deuteratedhydrofluorocarbon in combination with one or more perfluorocarbons.

Additionally, some of the compounds in Table 7 exist as multipleisomers, structural or optical. Single isomers or multiple isomers ofthe same compound may be used in any proportion to prepare the tracercompound. Further, single or multiple isomers of a given compound may becombined in any proportion with any number of other compounds to serveas a tracer blend.

The tracer compound or tracer blend may be present in the compositionsat a total concentration of about 50 parts per million by weight (ppm)to about 1000 ppm. Preferably, the tracer compound or tracer blend ispresent at a total concentration of about 50 ppm to about 500 ppm andmost preferably, the tracer compound or tracer blend is present at atotal concentration of about 100 ppm to about 300 ppm.

The compositions of the present invention may further comprise acompatibilizer selected from the group consisting of polyoxyalkyleneglycol ethers, amides, nitrites, ketones, chlorocarbons, esters,lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes. Thecompatibilizer is used to improve solubility of hydrofluorocarbonrefrigerants in conventional refrigeration lubricants. Refrigerationlubricants are needed to lubricate the compressor of a refrigeration,air-conditioning or heat pump apparatus. The lubricant must movethroughout the apparatus with the refrigerant in particular it mustreturn from the non-compressor zones to the compressor to continue tofunction as lubricant and avoid compressor failure.

Hydrofluorocarbon refrigerants are generally not compatible withconvention refrigeration lubricants such as mineral oils, alkylbenzenes,synthetic paraffins, synthetic napthenes and poly(alpha)olefins. Manyreplacement lubricants have been proposed, however, the polyalkyleneglycols, polyol esters and polyvinyl ethers, suggested for use withhydrofluorocarbon refrigerants are expensive and absorb water readily.Water in a refrigeration, air-conditioning system or heat pump can leadto corrosion and the formation of particles that may plug the capillarytubes and other small orifices in the system, ultimately causing systemfailure. Additionally, in existing equipment, time-consuming and costlyflushing procedures are required to change to a new lubricant.Therefore, it is desirable to continue to use the original lubricant ifpossible.

The compatibilizers of the present invention improve solubility of thehydrofluorocarbon refrigerants in conventional refrigeration lubricantsand thus improve oil return to the compressor.

Polyoxyalkylene glycol ether compatibilizers of the present inventionare represented by the formula R¹[(OR²)_(x)OR³]_(y), wherein: x is aninteger from 1-3; y is an integer from 1-4; R¹ is selected from hydrogenand aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and ybonding sites; R² is selected from aliphatic hydrocarbylene radicalshaving from 2 to 4 carbon atoms; R³ is selected from hydrogen andaliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbonatoms; at least one of R¹ and R³ is said hydrocarbon radical; andwherein said polyoxyalkylene glycol ethers have a molecular weight offrom about 100 to about 300 atomic mass units. As used herein, bondingsites mean radical sites available to form covalent bonds with otherradicals. Hydrocarbylene radicals mean divalent hydrocarbon radicals. Inthe present invention, preferred polyoxyalkylene glycol ethercompatibilizers are represented by R¹[(OR²)_(x)OR³]_(y): x is preferably1-2; y is preferably 1; R¹ and R³ are preferably independently selectedfrom hydrogen and aliphatic hydrocarbon radicals having 1 to 4 carbonatoms; R² is preferably selected from aliphatic hydrocarbylene radicalshaving from 2 or 3 carbon atoms, most preferably 3 carbon atoms; thepolyoxyalkylene glycol ether molecular weight is preferably from about100 to about 250 atomic mass units, most preferably from about 125 toabout 250 atomic mass units. The R¹ and R³ hydrocarbon radicals having 1to 6 carbon atoms may be linear, branched or cyclic. Representative R¹and R³ hydrocarbon radicals include methyl, ethyl, propyl, isopropyl,butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl,tert-pentyl, cyclopentyl, and cyclohexyl. Where free hydroxyl radicalson the present polyoxyalkylene glycol ether compatibilizers may beincompatible with certain compression refrigeration apparatus materialsof construction (e.g. Mylar®), R¹ and R³ are preferably aliphatichydrocarbon radicals having 1 to 4 carbon atoms, most preferably 1carbon atom. The R² aliphatic hydrocarbylene radicals having from 2 to 4carbon atoms form repeating oxyalkylene radicals —(OR²)_(x)— thatinclude oxyethylene radicals, oxypropylene radicals, and oxybutyleneradicals. The oxyalkylene radical comprising R² in one polyoxyalkyleneglycol ether compatibilizer molecule may be the same, or one moleculemay contain different R² oxyalkylene groups. The present polyoxyalkyleneglycol ether compatibilizers preferably comprise at least oneoxypropylene radical. Where R¹ is an aliphatic or alicyclic hydrocarbonradical having 1 to 6 carbon atoms and y bonding sites, the radical maybe linear, branched or cyclic. Representative R¹ aliphatic hydrocarbonradicals having two bonding sites include, for example, an ethyleneradical, a propylene radical, a butylene radical, a pentylene radical, ahexylene radical, a cyclopentylene radical and a cyclohexylene radical.Representative R¹ aliphatic hydrocarbon radicals having three or fourbonding sites include residues derived from polyalcohols, such astrimethylolpropane, glycerin, pentaerythritol,1,2,3-trihydroxycyclohexane and 1,3,5-trihydroxycyclohexane, by removingtheir hydroxyl radicals.

Representative polyoxyalkylene glycol ether compatibilizers include butare not limited to: CH₃OCH₂CH(CH₃)O(H or CH₃) (propylene glycol methyl(or dimethyl)ether), CH₃O[CH₂CH(CH₃)O]₂(H or CH₃) (dipropylene glycolmethyl (or dimethyl)ether), CH₃O[CH₂CH(CH₃)O]₃(H or CH₃) (tripropyleneglycol methyl (or dimethyl)ether), C₂H₅OCH₂CH(CH₃)O(H or C₂H₅)(propylene glycol ethyl (or diethyl)ether), C₂H₅O[CH₂CH(CH₃)O]₂(H orC₂H₅) (dipropylene glycol ethyl (or diethyl)ether),C₂H₅O[CH₂CH(CH₃)O]₃(H or C₂H₅) (tripropylene glycol ethyl (ordiethyl)ether), C₃H₇OCH₂CH(CH₃)O(H or C₃H₇) (propylene glycol n-propyl(or di-n-propyl)ether), C₃H₇O[CH₂CH(CH₃)O]₂(H or C₃H₇) (dipropyleneglycol n-propyl (or di-n-propyl)ether), C₃H₇O[CH₂CH(CH₃)O]₃(H or C₃H₇)(tripropylene glycol n-propyl (or di-n-propyl)ether), C₄H₉OCH₂CH(CH₃)OH(propylene glycol n-butyl ether), C₄H₉O[CH₂CH(CH₃)O]₂(H or C₄H₉)(dipropylene glycol n-butyl (or di-n-butyl)ether), C₄H₉O[CH₂CH(CH₃)O]₃(Hor C₄H₉) (tripropylene glycol n-butyl (or di-n-butyl)ether),(CH₃)₃COCH₂CH(CH₃)OH (propylene glycol t-butyl ether),(CH₃)₃CO[CH₂CH(CH₃)O]₂(H or (CH₃)₃) (dipropylene glycol t-butyl (ordi-t-butyl)ether), (CH₃)₃CO[CH₂CH(CH₃)O]₃(H or (CH₃)₃) (tripropyleneglycol t-butyl (or di-t-butyl)ether), C₅H₁₁OCH₂CH(CH₃)OH (propyleneglycol n-pentyl ether), C₄H₉OCH₂CH(C₂H₅)OH (butylene glycol n-butylether), C₄H₉O[CH₂CH(C₂H₅)O]₂H (dibutylene glycol n-butyl ether),trimethylolpropane tri-n-butyl ether (C₂H₅C(CH₂O(CH₂)₃CH₃)₃) andtrimethylolpropane di-n-butyl ether (C₂H₅C(CH₂OC(CH₂)₃CH₃)₂CH₂OH).

Amide compatibilizers of the present invention comprise thoserepresented by the formulae R¹C(O)NR²R³ and cyclo-[R⁴C(O)N(R⁵)], whereinR¹, R², R³ and R⁵ are independently selected from aliphatic andalicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; R⁴ isselected from aliphatic hydrocarbylene radicals having from 3 to 12carbon atoms; and wherein said amides have a molecular weight of fromabout 100 to about 300 atomic mass units. The molecular weight of saidamides is preferably from about 160 to about 250 atomic mass units. R¹,R², R³ and R⁵ may optionally include substituted hydrocarbon radicals,that is, radicals containing non-hydrocarbon substituents selected fromhalogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R¹,R², R³ and R⁵ may optionally include heteroatom-substituted hydrocarbonradicals, that is, radicals, which contain the atoms nitrogen (aza-),oxygen (oxa-) or sulfur (thia-) in a radical chain otherwise composed ofcarbon atoms. In general, no more than three non-hydrocarbonsubstituents and heteroatoms, and preferably no more than one, will bepresent for each 10 carbon atoms in R¹⁻³, and the presence of any suchnon-hydrocarbon substituents and heteroatoms must be considered inapplying the aforementioned molecular weight limitations. Preferredamide compatibilizers consist of carbon, hydrogen, nitrogen and oxygen.Representative R¹, R², R³ and R⁵ aliphatic and alicyclic hydrocarbonradicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl,sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl,cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyland their configurational isomers. A preferred embodiment of amidecompatibilizers are those wherein R⁴ in the aforementioned formulacyclo-[R⁴C(O)N(R⁵)—] may be represented by the hydrocarbylene radical(CR⁶R⁷)_(n), in other words, the formula: cyclo-[(CR⁶R⁷)_(n)C(O)N(R⁵)—]wherein: the previously-stated values for molecular weight apply; n isan integer from 3 to 5; R⁵ is a saturated hydrocarbon radical containing1 to 12 carbon atoms; R⁶ and R⁷ are independently selected (for each n)by the rules previously offered defining R¹⁻³. In the lactamsrepresented by the formula: cyclo-[(CR⁶R⁷)_(n)C(O)N(R⁵)—], all R⁶ and R⁷are preferably hydrogen, or contain a single saturated hydrocarbonradical among the n methylene units, and R⁵ is a saturated hydrocarbonradical containing 3 to 12 carbon atoms. For example, 1-(saturatedhydrocarbon radical)-5-methylpyrrolidin-2-ones.

Representative amide compatibilizers include but are not limited to:1-octylpyrrolidin-2-one, 1-decylpyrrolidin-2-one,1-octyl-5-methylpyrrolidin-2-one, 1-butylcaprolactam,1-cyclohexylpyrrolidin-2-one, 1-butyl-5-methylpiperid-2-one,1-pentyl-5-methylpiperid-2-one, 1-hexylcaprolactam,1-hexyl-5-methylpyrrolidin-2-one, 5-methyl-1-pentylpiperid-2-one,1,3-dimethylpiperid-2-one, 1-methylcaprolactam,1-butyl-pyrrolidin-2-one, 1,5-dimethylpiperid-2-one,1-decyl-5-methylpyrrolidin-2-one, 1-dodecylpyrrolid-2-one,N,N-dibutylformamide and N,N-diisopropylacetamide.

Ketone compatibilizers of the present invention comprise ketonesrepresented by the formula R¹C(O)R², wherein R¹ and R² are independentlyselected from aliphatic, alicyclic and aryl hydrocarbon radicals havingfrom 1 to 12 carbon atoms, and wherein said ketones have a molecularweight of from about 70 to about 300 atomic mass units. R¹ and R² insaid ketones are preferably independently selected from aliphatic andalicyclic hydrocarbon radicals having 1 to 9 carbon atoms. The molecularweight of said ketones is preferably from about 100 to 200 atomic massunits. R¹ and R² may together form a hydrocarbylene radical connectedand forming a five, six, or seven-membered ring cyclic ketone, forexample, cyclopentanone, cyclohexanone, and cycloheptanone. R¹ and R²may optionally include substituted hydrocarbon radicals, that is,radicals containing non-hydrocarbon substituents selected from halogens(e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R¹ and R² mayoptionally include heteroatom-substituted hydrocarbon radicals, that is,radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-)or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.In general, no more than three non-hydrocarbon substituents andheteroatoms, and preferably no more than one, will be present for each10 carbon atoms in R¹ and R², and the presence of any suchnon-hydrocarbon substituents and heteroatoms must be considered inapplying the aforementioned molecular weight limitations. RepresentativeR¹ and R² aliphatic, alicyclic and aryl hydrocarbon radicals in thegeneral formula R¹C(O)R² include methyl, ethyl, propyl, isopropyl,butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl,tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl and their configurational isomers, as well as phenyl,benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.

Representative ketone compatibilizers include but are not limited to:2-butanone, 2-pentanone, acetophenone, butyrophenone, hexanophenone,cyclohexanone, cycloheptanone, 2-heptanone, 3-heptanone,5-methyl-2-hexanone, 2-octanone, 3-octanone, diisobutyl ketone,4-ethylcyclohexanone, 2-nonanone, 5-nonanone, 2-decanone, 4-decanone,2-decalone, 2-tridecanone, dihexyl ketone and dicyclohexyl ketone.

Nitrile compatibilizers of the present invention comprise nitrilesrepresented by the formula R¹CN, wherein R¹ is selected from aliphatic,alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms,and wherein said nitriles have a molecular weight of from about 90 toabout 200 atomic mass units. R¹ in said nitrile compatibilizers ispreferably selected from aliphatic and alicyclic hydrocarbon radicalshaving 8 to 10 carbon atoms. The molecular weight of said nitrilecompatibilizers is preferably from about 120 to about 140 atomic massunits. R¹ may optionally include substituted hydrocarbon radicals, thatis, radicals containing non-hydrocarbon substituents selected fromhalogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R¹ mayoptionally include heteroatom-substituted hydrocarbon radicals, that is,radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-)or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.In general, no more than three non-hydrocarbon substituents andheteroatoms, and preferably no more than one, will be present for each10 carbon atoms in R¹, and the presence of any such non-hydrocarbonsubstituents and heteroatoms must be considered in applying theaforementioned molecular weight limitations. Representative R¹aliphatic, alicyclic and aryl hydrocarbon radicals in the generalformula R¹CN include pentyl, isopentyl, neopentyl, tert-pentyl,cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyland their configurational isomers, as well as phenyl, benzyl, cumenyl,mesityl, tolyl, xylyl and phenethyl.

Representative nitrile compatibilizers include but are not limited to:1-cyanopentane, 2,2-dimethyl-4-cyanopentane, 1-cyanohexane,1-cyanoheptane, 1-cyanooctane, 2-cyanooctane, 1-cyanononane,1-cyanodecane, 2-cyanodecane, 1-cyanoundecane and 1-cyanododecane.

Chlorocarbon compatibilizers of the present invention comprisechlorocarbons represented by the formula RCl_(x), wherein; x is selectedfrom the integers 1 or 2; R is selected from aliphatic and alicyclichydrocarbon radicals having 1 to 12 carbon atoms; and wherein saidchlorocarbons have a molecular weight of from about 100 to about 200atomic mass units. The molecular weight of said chlorocarboncompatibilizers is preferably from about 120 to 150 atomic mass units.Representative R aliphatic and alicyclic hydrocarbon radicals in thegeneral formula RCl_(x) include methyl, ethyl, propyl, isopropyl, butyl,isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl,tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl and their configurational isomers.

Representative chlorocarbon compatibilizers include but are not limitedto: 3-(chloromethyl)pentane, 3-chloro-3-methylpentane, 1-chlorohexane,1,6-dichlorohexane, 1-chloroheptane, 1-chlorooctane, 1-chlorononane,1-chlorodecane, and 1,1,1-trichlorodecane.

Ester compatibilizers of the present invention comprise estersrepresented by the general formula R¹CO₂R², wherein R¹ and R² areindependently selected from linear and cyclic, saturated andunsaturated, alkyl and aryl radicals. Preferred esters consistessentially of the elements C, H and O, have a molecular weight of fromabout 80 to about 550 atomic mass units.

Representative esters include but are not limited to:(CH₃)₂CHCH₂OOC(CH₂)₂₋₄OCOCH₂CH(CH₃)₂ (diisobutyl dibasic ester), ethylhexanoate, ethyl heptanoate, n-butyl propionate, n-propyl propionate,ethyl benzoate, di-n-propyl phthalate, benzoic acid ethoxyethyl ester,dipropyl carbonate, “Exxate 700” (a commercial C₇ alkyl acetate),“Exxate 800” (a commercial C₈ alkyl acetate), dibutyl phthalate, andtert-butyl acetate.

Lactone compatibilizers of the present invention comprise lactonesrepresented by structures [A], [B], and [C]:

These lactones contain the functional group —CO₂— in a ring of six (A),or preferably five atoms (B), wherein for structures [A] and [B], R₁through R₈ are independently selected from hydrogen or linear, branched,cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. EachR₁ though R₈ may be connected forming a ring with another R₁ through R₈.The lactone may have an exocyclic alkylidene group as in structure [C],wherein R₁ through R₆ are independently selected from hydrogen orlinear, branched, cyclic, bicyclic, saturated and unsaturatedhydrocarbyl radicals. Each R₁ though R₆ may be connected forming a ringwith another R₁ through R₆. The lactone compatibilizers have a molecularweight range of from about 100 to about 300 atomic mass units, preferredfrom about 100 to about 200 atomic mass units.

Representative lactone compatibilizers include but are not limited tothe compounds listed in Table 8.

TABLE 8 Molecular Molecular Additive Molecular Structure Formula Weight(amu) (E,Z)-3-ethylidene-5- methyl-dihydro-furan-2- one

C₇H₁₀O₂ 126 (E,Z)-3-propylidene-5- methyl-dihydro-furan-2- one

C₈H₁₂O₂ 140 (E,Z)-3-butylidene-5- methyl-dihydro-furan-2- one

C₉H₁₄O₂ 154 (E,Z)-3-pentylidene-5- methyl-dihydro-furan-2- one

C₁₀H₁₆O₂ 168 (E,Z)-3-Hexylidene-5- methyl-dihydro-furan-2- one

C₁₁H₁₈O₂ 182 (E,Z)-3-Heptylidene-5- methyl-dihydro-furan-2- one

C₁₂H₂₀O₂ 196 (E,Z)-3-octylidene-5- methyl-dihydro-furan-2- one

C₁₃H₂₂O₂ 210 (E,Z)-3-nonylidene-5- methyl-dihydro-furan-2- one

C₁₄H₂₄O₂ 224 (E,Z)-3-decylidene-5- methyl-dihydro-furan-2- one

C₁₅H₂₆O₂ 238 (E,Z)-3-(3,5,5- trimethylhexylidene)-5-methyl-dihydrofuran-2- one

C₁₄H₂₄O₂ 224 (E,Z)-3- cyclohexylmethylidene- 5-methyl-dihydrofuran-2-one

C₁₂H₁₈O₂ 194 gamma-octalactone

C₈H₁₄O₂ 142 gamma-nonalactone

C₉H₁₆O₂ 156 gamma-decalactone

C₁₀H₁₈O₂ 170 gamma-undecalactone

C₁₁H₂₀O₂ 184 gamma-dodecalactone

C₁₂H₂₂O₂ 198 3-hexyldihydro-furan-2- one

C₁₀H₁₈O₂ 170 3-heptyldihydro-furan- 2-one

C₁₁H₂₀O₂ 184 cis-3-ethyl-5-methyl- dihydro-furan-2-one

C₇H₁₂O₂ 128 cis-(3-propyl-5-methyl)- dihydro-furan-2-one

C₈H₁₄O₂ 142 cis-(3-butyl-5-methyl)- dihydro-furan-2-one

C₉H₁₆O₂ 156 cis-(3-pentyl-5-methyl)- dihydro-furan-2-one

C₁₀H₁₈O₂ 170 cis-3-hexyl-5-methyl- dihydro-furan-2-one

C₁₁H₂₀O₂ 184 cis-3-heptyl-5-methyl- dihydro-furan-2-one

C₁₂H₂₂O₂ 198 cis-3-octyl-5-methyl- dihydro-furan-2-one

C₁₃H₂₄O₂ 212 cis-3-(3,5,5- trimethylhexyl )-5- methyl-dihydro-furan-2-one

C₁₄H₂₄O₂ 226 cis-3-cyclohexylmethyl- 5-methyl-dihydro-furan- 2-one

C₁₂H₂₀O₂ 196 5-methyl-5-hexyl- dihydro-furan-2-one

C₁₁H₂₀O₂ 184 5-methyl-5-octyl- dihydro-furan-2-one

C₁₃H₂₄O₂ 212 Hexahydro- isobenzofuran-1-one

C₈H₁₂O₂ 140 delta-decalactone

C₁₀H₁₈O₂ 170 delta-undecalactone

C₁₁H₂₀O₂ 184 delta-dodecalactone

C₁₂H₂₂O₂ 198 mixture of 4-hexyl- dihydrofuran-2-one and3-hexyl-dihydro-furan- 2-one

C₁₀H₁₈O₂ 170

Lactone compatibilizers generally have a kinematic viscosity of lessthan about 7 centistokes at 40° C. For instance, gamma-undecalactone haskinematic viscosity of 5.4 centistokes andcis-(3-hexyl-5-methyl)dihydrofuran-2-one has viscosity of 4.5centistokes both at 40° C. Lactone compatibilizers may be availablecommercially or prepared by methods as described in U.S. patentapplication Ser. No. 10/910,495 filed Aug. 3, 2004, incorporated hereinby reference.

Aryl ether compatibilizers of the present invention further comprisearyl ethers represented by the formula R¹OR², wherein: R¹ is selectedfrom aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R² isselected from aliphatic hydrocarbon radicals having from 1 to 4 carbonatoms; and wherein said aryl ethers have a molecular weight of fromabout 100 to about 150 atomic mass units. Representative R¹ arylradicals in the general formula R¹OR² include phenyl, biphenyl, cumenyl,mesityl, tolyl, xylyl, naphthyl and pyridyl. Representative R² aliphatichydrocarbon radicals in the general formula R¹OR² include methyl, ethyl,propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.Representative aromatic ether compatibilizers include but are notlimited to: methyl phenyl ether (anisole), 1,3-dimethyoxybenzene, ethylphenyl ether and butyl phenyl ether.

Fluoroether compatibilizers of the present invention comprise thoserepresented by the general formula R¹OCF₂CF₂H, wherein R¹ is selectedfrom aliphatic, alicyclic, and aromatic hydrocarbon radicals having fromabout 5 to about 15 carbon atoms, preferably primary, linear, saturated,alkyl radicals. Representative fluoroether compatibilizers include butare not limited to: C₈H₁₇OCF₂CF₂H and C₆H₁₃OCF₂CF₂H. It should be notedthat if the refrigerant is a fluoroether, then the compatibilizer maynot be the same fluoroether.

Fluoroether compatibilizers may further comprise ethers derived fromfluoroolefins and polyols. The fluoroolefins may be of the type CF₂═CXY,wherein X is hydrogen, chlorine or fluorine, and Y is chlorine,fluorine, CF₃ or OR_(f), wherein R_(f) is CF₃, C₂F₅, or C₃F₇.Representative fluoroolefins are tetrafluoroethylene,chlorotrifluoroethylene, hexafluoropropylene, and perfluoromethylvinylether. The polyols may be linear or branched. Linear polyols may be ofthe type HOCH₂(CHOH)_(x)(CRR′)_(y)CH₂OH, wherein R and R′ are hydrogen,or CH₃, or C₂H₅ and wherein x is an integer from 0-4, and y is aninteger from 0-4. Branched polyols may be of the typeC(OH)_(t)(R)_(u)(CH₂OH)_(v)[(CH₂)_(m)CH₂OH]_(w), wherein R may behydrogen, CH₃ or C₂H₅, m may be an integer from 0 to 3, t and u may be 0or 1, v and w are integers from 0 to 4, and also wherein t+u+v+w=4.Representative polyols are trimethylol propane, pentaerythritol,butanediol, and ethylene glycol.

1,1,1-trifluoroalkane compatibilizers of the present invention comprise1,1,1-trifluoroalkanes represented by the general formula CF₃R¹, whereinR¹ is selected from aliphatic and alicyclic hydrocarbon radicals havingfrom about 5 to about 15 carbon atoms, preferably primary, linear,saturated, alkyl radicals. Representative 1,1,1-trifluoroalkanecompatibilizers include but are not limited to: 1,1,1-trifluorohexaneand 1,1,1-trifluorododecane.

By effective amount of compatibilizer is meant that amount ofcompatibilizer that leads to efficient solubilizing of the lubricant inthe composition and thus provides adequate oil return to optimizeoperation of the refrigeration, air-conditioning or heat pump apparatus.

The compositions of the present invention will typically contain fromabout 0.1 to about 40 weight percent, preferably from about 0.2 to about20 weight percent, and most preferably from about 0.3 to about 10 weightpercent compatibilizer in the compositions of the present invention.

The present invention further relates to a method for improvingoil-return to the compressor in a compression refrigeration,air-conditioning or heat pump apparatus, said method comprising using acomposition of the present invention comprising a compatibilizer in saidapparatus. The compatibilizer is selected from the group consisting ofhydrocarbons, dimethylether, polyoxyalkylene glycol ethers, amides,ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers,hydrofluoroethers, hydrocarbon ethers and 1,1,11-trifluoroalkanes.

The present invention further relates to a method of solubilizing arefrigerant or heat transfer fluid composition comprising thecompositions of the present invention in a refrigeration lubricantselected from the group consisting of mineral oils, alkylbenzenes,synthetic paraffins, synthetic napthenes, and poly(alpha)olefins,wherein said method comprises contacting said lubricant with saidcomposition in the presence of an effective amount of a compatibilizer,wherein said compatibilizer is selected from the group consisting ofpolyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons,esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes.

The compositions of the present invention may further comprise anultra-violet (UV) dye and optionally a solubilizing agent. The UV dye isa useful component for detecting leaks of the composition by permittingone to observe the fluorescence of the dye in the composition at a leakpoint or in the vicinity of refrigeration, air-conditioning, or heatpump apparatus. One may observe the fluorescence of the dye under anultra-violet light. Solubilizing agents may be needed due to poorsolubility of such UV dyes in some compositions.

By “ultra-violet” dye is meant a UV fluorescent composition that absorbslight in the ultra-violet or “near” ultra-violet region of theelectromagnetic spectrum. The fluorescence produced by the UVfluorescent dye under illumination by a UV light that emits radiationwith wavelength anywhere from 10 nanometer to 750 nanometer may bedetected. Therefore, if a composition containing such a UV fluorescentdye is leaking from a given point in a refrigeration, air-conditioning,or heat pump apparatus, the fluorescence can be detected at the leakpoint. Such UV fluorescent dyes include but are not limited tonaphthalimides, perylenes, coumarins, anthracenes, phenanthracenes,xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, andderivatives or combinations thereof.

In accordance with the present invention, there is provided a method fordetecting the composition of the present invention comprising the dye asdescribed in the previous sentence in a compression refrigeration, airconditioning or heat pump apparatus. This method comprises providing thecomposition to the apparatus and providing a suitable means fordetecting this composition at a leak point or in the vicinity of theapparatus.

Solubilizing agents of the present invention comprise at least onecompound selected from the group consisting of hydrocarbons, hydrocarbonethers, dimethylether, polyoxyalkylene glycol ethers, amides, nitriles,ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and1,1,1-trifluoroalkanes. The polyoxyalkylene glycol ethers, amides,nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers,fluoroethers and 1,1,1-trifluoroalkanes solubilizing agents have beendefined previously herein as being compatibilizers for use withconventional refrigeration lubricants.

Hydrocarbon solubilizing agents of the present invention comprisehydrocarbons including straight chained, branched chain or cyclicalkanes or alkenes containing 5 or fewer carbon atoms and only hydrogenwith no other functional groups. Representative hydrocarbon solubilizingagents comprise propane, propylene, cyclopropane, n-butane, isobutane,2-methylbutane and n-pentane. It should be noted that if the compositioncontains a hydrocarbon, then the solubilizing agent may not be the samehydrocarbon.

Hydrocarbon ether solubilizing agents of the present invention compriseethers containing only carbon, hydrogen and oxygen, such as dimethylether (DME).

Solubilizing agents of the present invention may be present as a singlecompound, or may be present as a mixture of more than one solubilizingagent. Mixtures of solubilizing agents may contain two solubilizingagents from the same class of compounds, say two lactones, or twosolubilizing agents from two different classes, such as a lactone and apolyoxyalkylene glycol ether.

In the present compositions comprising refrigerant and UV fluorescentdye, or comprising heat transfer fluid and UV fluorescent dye, fromabout 0.001 weight percent to about 1.0 weight percent of thecomposition is UV dye, preferably from about 0.005 weight percent toabout 0.5 weight percent, and most preferably from 0.01 weight percentto about 0.25 weight percent.

Solubilizing agents such as ketones may have an objectionable odor,which can be masked by addition of an odor masking agent or fragrance.Typical examples of odor masking agents or fragrances may includeEvergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint, Floral or OrangePeel all commercially available, as well as d-limonene and pinene. Suchodor masking agents may be used at concentrations of from about 0.001%to as much as about 15% by weight based on the combined weight of odormasking agent and solubilizing agent.

Solubility of these UV fluorescent dyes in the compositions of thepresent invention may be poor. Therefore, methods for introducing thesedyes into the refrigeration, air-conditioning, or heat pump apparatushave been awkward, costly and time consuming. U.S. Pat. No. RE 36,951describes a method, which utilizes a dye powder, solid pellet or slurryof dye that may be inserted into a component of the refrigeration,air-conditioning, or heat pump apparatus. As refrigerant and lubricantare circulated through the apparatus, the dye is dissolved or dispersedand carried throughout the apparatus. Numerous other methods forintroducing dye into a refrigeration or air conditioning apparatus aredescribed in the literature.

Ideally, the UV fluorescent dye could be dissolved in the refrigerantitself thereby not requiring any specialized method for introduction tothe refrigeration, air conditioning apparatus, or heat pump. The presentinvention relates to compositions including UV fluorescent dye, whichmay be introduced into the system as a solution in the refrigerant. Theinventive compositions will allow the storage and transport ofdye-containing compositions even at low temperatures while maintainingthe dye in solution.

In the present compositions comprising refrigerant, UV fluorescent dyeand solubilizing agent, or comprising heat transfer fluid and UVfluorescent dye and solubilizing agent, from about 1 to about 50 weightpercent, preferably from about 2 to about 25 weight percent, and mostpreferably from about 5 to about 15 weight percent of the combinedcomposition is solubilizing agent. In the compositions of the presentinvention the UV fluorescent dye is present in a concentration fromabout 0.001 weight percent to about 1.0 weight percent, preferably from0.005 weight percent to about 0.5 weight percent, and most preferablyfrom 0.01 weight percent to about 0.25 weight percent.

The present invention further relates to a method of using thecompositions further comprising ultraviolet fluorescent dye, andoptionally, solubilizing agent, in refrigeration, air-conditioning, orheat pump apparatus. The method comprises introducing the compositioninto the refrigeration, air-conditioning, or heat pump apparatus. Thismay be done by dissolving the UV fluorescent dye in the composition inthe presence of a solubilizing agent and introducing the combinationinto the apparatus. Alternatively, this may be done by combiningsolubilizing agent and UV fluorescent dye and introducing saidcombination into refrigeration or air-conditioning apparatus containingrefrigerant and/or heat transfer fluid. The resulting composition may beused in the refrigeration, air-conditioning, or heat pump apparatus.

The present invention further relates to a method of using thecompositions comprising ultraviolet fluorescent dye to detect leaks. Thepresence of the dye in the compositions allows for detection of leakingrefrigerant in a refrigeration, air-conditioning, or heat pumpapparatus. Leak detection helps to address, resolve or preventinefficient operation of the apparatus or system or equipment failure.Leak detection also helps one contain chemicals used in the operation ofthe apparatus.

The method comprises providing the composition according to the presentinvention comprising refrigerant, ultra-violet fluorescent dye, asdescribed herein, and optionally, a solubilizing agent as describedherein, to refrigeration, air-conditioning, or heat pump apparatus andemploying a suitable means for detecting the UV fluorescentdye-containing refrigerant at a leak point or in the vicinity of theapparatus. Suitable means for detecting the dye include, but are notlimited to, ultra-violet lamps, often referred to as a “black light” or“blue light”. Such ultra-violet lamps are commercially available fromnumerous sources specifically designed for this purpose. Once theultra-violet fluorescent dye containing composition has been introducedto the refrigeration, air-conditioning, or heat pump apparatus and hasbeen allowed to circulate throughout the system, a leak can be found byshining said ultra-violet lamp on the apparatus and observing thefluorescence of the dye in the vicinity of any leak point.

The present invention further relates to a method for replacing a highGWP refrigerant in a refrigeration, air-conditioning, or heat pumpapparatus, wherein said high GWP refrigerant is selected from the groupconsisting of R134a, R22, R11, R245fa, R114, R236fa, R124, R410A, R407C,R417A, R422A, R422B, R422C and R422D, R507A, and R404A, said methodcomprising providing a composition of the present invention to saidrefrigeration, air-conditioning, or heat pump apparatus that uses, usedor is designed to use said high GWP refrigerant.

In a particular embodiment of the method as described in the paragraphabove the high GWP refrigerant is selected from the group consisting ofR134a, R22, R123, R11, R245fa, R114, R236fa, R124, R12, R410A, R407C,R417A, R422A, R422B, R422C and R422D, R507A, R502, and R404A asdescribed above. The method further comprises providing a composition tosaid refrigeration, air-conditioning, or heat pump apparatus that uses,used or designed to use said high GWP refrigerant, wherein thecomposition is selected from the group consisting of: about 1 weightpercent to about 99 weight percent HFC-1225ye and about 99 weightpercent to about 1 weight percent HFC-152a; about 1 weight percent toabout 99 weight percent HFC-1225ye and about 99 weight percent to about1 weight percent HFC-1234yf; about 1 weight percent to about 99 weightpercent HFC-1225ye and about 99 weight percent to about 1 weight percenttrans-HFC-1234ze; about 1 weight percent to about 99 weight percentHFC-1225ye and about 99 weight percent to about 1 weight percentHFC-1243zf; about 1 weight percent to about 99 weight percenttrans-HFC-1234ze and about 99 weight percent to about 1 weight percentHFC-134a; about 1 weight percent to about 99 weight percenttrans-HFC-1234ze and about 99 weight percent to about 1 weight percentHFC-152a; about 1 weight percent to about 99 weight percenttrans-HFC-1234ze and about 99 weight percent to about 1 weight percentHFC-227ea; and about 1 weight percent to about 99 weight percenttrans-HFC-1234ze and about 99 weight percent to about 1 weight percentCF₃I.

Vapor-compression refrigeration, air-conditioning, or heat pump systemsinclude an evaporator, a compressor, a condenser, and an expansiondevice. A vapor-compression cycle re-uses refrigerant in multiple stepsproducing a cooling effect in one step and a heating effect in adifferent step. The cycle can be described simply as follows. Liquidrefrigerant enters an evaporator through an expansion device, and theliquid refrigerant boils in the evaporator at a low temperature to forma gas and produce cooling. The low-pressure gas enters a compressorwhere the gas is compressed to raise its pressure and temperature. Thehigher-pressure (compressed) gaseous refrigerant then enters thecondenser in which the refrigerant condenses and discharges its heat tothe environment. The refrigerant returns to the expansion device throughwhich the liquid expands from the higher-pressure level in the condenserto the low-pressure level in the evaporator, thus repeating the cycle.

According to the present invention, there is provided a refrigeration,air-conditioning or heat pump apparatus containing a composition of thepresent invention. In particular, the refrigeration or air-conditioningapparatus may be a mobile apparatus.

As used herein, mobile refrigeration apparatus or mobileair-conditioning apparatus refers to any refrigeration orair-conditioning apparatus incorporated into a transportation unit forthe road, rail, sea or air. In addition, apparatus, which are meant toprovide refrigeration or air-conditioning for a system independent ofany moving carrier, known as “intermodal” systems, are included in thepresent invention. Such intermodal systems include “containers”(combined sea/land transport) as well as “swap bodies” (combined roadand rail transport). The present invention is particularly useful forroad transport refrigerating or air-conditioning apparatus, such asautomobile air-conditioning apparatus or refrigerated road transportequipment.

The compositions of the present invention may also be useful instationary air-conditioning and heat pumps, e.g. chillers, hightemperature heat pumps, residential and light commercial and commercialair-conditioning systems. In stationary refrigeration applications, thepresent compositions may be useful in equipment such as domesticrefrigerators, ice machines, walk-in and reach-in coolers and freezers,and supermarket systems.

The present invention further relates to a method of producing coolingcomprising evaporating any of the compositions of the present inventionin the vicinity of a body to be cooled, and thereafter condensing saidcomposition.

The present invention further relates to a method of producing heatcomprising condensing any of the compositions of the present inventionin the vicinity of a body to be heated, and thereafter evaporating saidcompositions.

The present invention further relates to a refrigeration,air-conditioning, or heat pump apparatus containing a composition of thepresent invention wherein said composition comprises at least onefluoroolefin.

The present invention further relates to a mobile air-conditioningapparatus containing a composition of the present invention wherein saidcomposition comprises at least one fluoroolefin.

The present invention further relates to a method for early detection ofa refrigerant leak in a refrigeration, air-conditioning or heat pumpapparatus. The method comprising using a non-azeotropic composition insaid apparatus, and monitoring for a reduction in cooling performance.The non-azeotropic compositions will fractionate upon leakage from arefrigeration, air-conditioning or heat pump apparatus and the lowerboiling (higher vapor pressure) component will leak out of the apparatusfirst. When this occurs, if the lower boiling component in thatcomposition provides the majority of the refrigeration capacity, therewill be a marked reduction in the capacity and thus performance of theapparatus. In an automobile air-conditioning system, as an example, thepassengers in the automobile will detect a reduction in the coolingcapability of the system. This reduction in cooling capability can beinterpreted to mean that refrigerant is being leaked and that the systemrequires repair.

The present invention further relates to a method of using thecomposition of the present invention as a heat transfer fluidcomposition. The method comprises transporting said composition from aheat source to a heat sink.

Heat transfer fluids are utilized to transfer, move or remove heat fromone space, location, object or body to a different space, location,object or body by radiation, conduction, or convection. A heat transferfluid may function as a secondary coolant by providing means of transferfor cooling (or heating) from a remote refrigeration (or heating)system. In some systems, the heat transfer fluid may remain in aconstant state throughout the transfer process (i.e., not evaporate orcondense). Alternatively, evaporative cooling processes may utilize heattransfer fluids as well.

A heat source may be defined as any space, location, object or body fromwhich it is desirable to transfer, move or remove heat. Examples of heatsources may be spaces (open or enclosed) requiring refrigeration orcooling, such as refrigerator or freezer cases in a supermarket,building spaces requiring air-conditioning, or the passenger compartmentof an automobile requiring air-conditioning. A heat sink may be definedas any space, location, object or body capable of absorbing heat. Avapor compression refrigeration system is one example of such a heatsink.

In certain embodiments, particular combinations of the componentsdescribed above may be used, and in particular weight percentages. Thefollowing compositions are meant to be exemplary of such embodiments,without limiting the scope of the compositions of the present inventionto the following.

In one embodiment, the present invention relates to a compositioncomprising: at least one lubricant selected from the group consisting ofpolyol esters, polyalkylene glycol, polyvinyl ethers, mineral oils,alkylbenzenes, synthetic paraffins, synthetic napthenes, andpoly(alpha)olefins; and a composition selected from the group consistingof: about 1 weight percent to about 99 weight percent HFC-1225ye andabout 99 weight percent to about 1 weight percent HFC-152a; about 1weight percent to about 99 weight percent HFC-1225ye and about 99 weightpercent to about 1 weight percent HFC-1234yf; about 1 weight percent toabout 99 weight percent HFC-1225ye and about 99 weight percent to about1 weight percent trans-HFC-1234ze; about 1 weight percent to about 99weight percent HFC-1225ye and about 99 weight percent to about 1 weightpercent HFC-1243zf; about 1 weight percent to about 99 weight percenttrans-HFC-1234ze and about 99 weight percent to about 1 weight percentHFC-134a; about 1 weight percent to about 99 weight percenttrans-HFC-1234ze and about 99 weight percent to about 1 weight percentHFC-152a; about 1 weight percent to about 99 weight percenttrans-HFC-1234ze and about 99 weight percent to about 1 weight percentHFC-227ea; and about 1 weight percent to about 99 weight percenttrans-HFC-1234ze and about 99 weight percent to about 1 weight percentCF₃I.

In another embodiment, the present invention relates to a compositioncomprising: a refrigerant or heat transfer fluid composition selectedfrom the group consisting of: about 1 weight percent to about 99 weightpercent HFC-1225ye and about 99 weight percent to about 1 weight percentHFC-152a; about 1 weight percent to about 99 weight percent HFC-1225yeand about 99 weight percent to about 1 weight percent HFC-1234yf; about1 weight percent to about 99 weight percent HFC-1225ye and about 99weight percent to about 1 weight percent trans-HFC-1234ze; about 1weight percent to about 99 weight percent HFC-1225ye and about 99 weightpercent to about 1 weight percent HFC-1243zf; about 1 weight percent toabout 99 weight percent trans-HFC-1234ze and about 99 weight percent toabout 1 weight percent HFC-134a; about 1 weight percent to about 99weight percent trans-HFC-1234ze and about 99 weight percent to about 1weight percent HFC-152a; about 1 weight percent to about 99 weightpercent trans-HFC-1234ze and about 99 weight percent to about 1 weightpercent HFC-227ea; and about 1 weight percent to about 99 weight percenttrans-HFC-1234ze and about 99 weight percent to about 1 weight percentCF₃I. The composition also comprises a compatibilizer selected from thegroup consisting of: i) polyoxyalkylene glycol ethers represented by theformula R¹[(OR²)_(x)OR³]_(y), wherein: x is an integer from 1 to 3; y isan integer from 1 to 4; R¹ is selected from hydrogen and aliphatichydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R²is selected from aliphatic hydrocarbylene radicals having from 2 to 4carbon atoms; R³ is selected from hydrogen, and aliphatic and alicyclichydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R¹and R³ is selected from said hydrocarbon radicals; and wherein saidpolyoxyalkylene glycol ethers have a molecular weight of from about 100to about 300 atomic mass units; ii) amides represented by the formulaeR¹C(O)NR²R³ and cyclo-[R⁴CON(R⁵)—], wherein R¹, R², R³ and R⁵ areindependently selected from aliphatic and alicyclic hydrocarbon radicalshaving from 1 to 12 carbon atoms, and at most one aromatic radicalhaving from 6 to 12 carbon atoms; R⁴ is selected from aliphatichydrocarbylene radicals having from 3 to 12 carbon atoms; and whereinsaid amides have a molecular weight of from about 100 to about 300atomic mass units; iii) ketones represented by the formula R¹C(O)R²,wherein R¹ and R² are independently selected from aliphatic, alicyclicand aryl hydrocarbon radicals having from 1 to 12 carbon atoms, andwherein said ketones have a molecular weight of from about 70 to about300 atomic mass units; iv) nitriles represented by the formula R¹CN,wherein R¹ is selected from aliphatic, alicyclic or aryl hydrocarbonradicals having from 5 to 12 carbon atoms, and wherein said nitrileshave a molecular weight of from about 90 to about 200 atomic mass units;v) chlorocarbons represented by the formula RCl_(x), wherein; x is 1 or2; R is selected from aliphatic and alicyclic hydrocarbon radicalshaving from 1 to 12 carbon atoms; and wherein said chlorocarbons have amolecular weight of from about 100 to about 200 atomic mass units; vi)aryl ethers represented by the formula R¹OR², wherein: R¹ is selectedfrom aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R² isselected from aliphatic hydrocarbon radicals having from 1 to 4 carbonatoms; and wherein said aryl ethers have a molecular weight of fromabout 100 to about 150 atomic mass units; vii) 1,1,1-trifluoroalkanesrepresented by the formula CF₃R¹, wherein R¹ is selected from aliphaticand alicyclic hydrocarbon radicals having from about 5 to about 15carbon atoms; viii) fluoroethers represented by the formula R¹OCF₂CF₂H,wherein R¹ is selected from aliphatic, alicyclic, and aromatichydrocarbon radicals having from about 5 to about 15 carbon atoms; orwherein said fluoroethers are derived from fluoroolefins and polyols,wherein said fluoroolefins are of the type CF₂═CXY, wherein X ishydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF₃ orOR_(f), wherein R_(f) is CF₃, C₂F₅, or C₃F₇; and said polyols are linearor branched, wherein said linear polyols are of the typeHOCH₂(CHOH)_(x)(CRR′)_(y)CH₂OH, wherein R and R′ are hydrogen, CH₃ orC₂H₅, x is an integer from 0-4, y is an integer from 0-3 and z is eitherzero or 1, and said branched polyols are of the typeC(OH)_(t)(R)_(u)(CH₂OH)_(v)[(CH₂)_(m)CH₂OH]_(w), wherein R may behydrogen, CH₃ or C₂H₅, m is an integer from 0 to 3, t and u are 0 or 1,v and w are integers from 0 to 4, and also wherein t+u+v+w=4; and ix)lactones represented by structures [B], [C], and [D]:

wherein, R₁ through R₈ are independently selected from hydrogen, linear,branched, cyclic, bicyclic, saturated and unsaturated hydrocarbylradicals; and the molecular weight is from about 100 to about 300correct atomic mass units; and x) esters represented by the generalformula R¹CO₂R², wherein R¹ and R² are independently selected fromlinear and cyclic, saturated and unsaturated, alkyl and aryl radicals;and wherein said esters have a molecular weight of from about 80 toabout 550 atomic mass units.

According to the present invention, there is provided a refrigeration,air-conditioning or heat pump apparatus containing a composition asdescribed in the paragraph above. In particular, the refrigeration orair-conditioning apparatus may be a mobile apparatus.

Further in accordance with this particular embodiment, the presentinvention relates to a method for improving oil-return to a compressorin a compression refrigeration, air-conditioning or heat pump apparatus.The method comprises using the composition as described in the paragraphabove in the compression refrigeration, air-conditioning or heat pumpapparatus.

In another particular embodiment, the present invention relates to acomposition comprising (a) at least one ultra-violet fluorescent dyeselected from the group consisting of naphthalimides, perylenes,coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes,naphthoxanthenes, fluoresceins, derivatives of said dye and combinationsthereof; and (b) a composition selected from the group consisting of:about 1 weight percent to about 99 weight percent HFC-1225ye and about99 weight percent to about 1 weight percent HFC-152a; about 1 weightpercent to about 99 weight percent HFC-1225ye and about 99 weightpercent to about 1 weight percent HFC-1234yf; about 1 weight percent toabout 99 weight percent HFC-1225ye and about 99 weight percent to about1 weight percent trans-HFC-1234ze; about 1 weight percent to about 99weight percent HFC-1225ye and about 99 weight percent to about 1 weightpercent HFC-1243zf; about 1 weight percent to about 99 weight percenttrans-HFC-1234ze and about 99 weight percent to about 1 weight percentHFC-134a; about 1 weight percent to about 99 weight percenttrans-HFC-1234ze and about 99 weight percent to about 1 weight percentHFC-152a; about 1 weight percent to about 99 weight percenttrans-HFC-1234ze and about 99 weight percent to about 1 weight percentHFC-227ea; and about 1 weight percent to about 99 weight percenttrans-HFC-1234ze and about 99 weight percent to about 1 weight percentCF₃I.

In accordance with the present invention, there is provided a method fordetecting the composition comprising the dye as described in theprevious paragraph in a compression refrigeration, air conditioning orheat pump apparatus. This method comprises providing the composition tothe apparatus and providing a suitable means for detecting thiscomposition at a leak point or in the vicinity of the apparatus.

According to the present invention, there is provided a refrigeration,air-conditioning or heat pump apparatus containing a composition asdescribed two paragraphs above. In particular, the refrigeration orair-conditioning apparatus may be a mobile apparatus.

Further in accordance with this particular embodiment, the compositionincluding (a) and (b) described three paragraphs above further includesa solubilizing agent selected from the group consisting of hydrocarbons,dimethylether, polyoxyalkylene glycol ethers, amides, ketones, nitriles,chlorocarbons, esters, lactones, aryl ethers, hydrofluoroethers and1,1,1-trifluoroalkanes.

In accordance with the present invention, there is provided a method fordetecting the composition comprising the dye as described in theprevious paragraph in a compression refrigeration, air conditioning orheat pump apparatus. This method comprises providing the composition tothe apparatus and providing a suitable means for detecting thiscomposition at a leak point or in the vicinity of the apparatus.

The solubilizing agent of the composition described in the paragraphabove is selected from the group consisting of: i) polyoxyalkyleneglycol ethers represented by the formula R¹[(OR²)_(x)OR³]_(y), wherein:x is an integer from 1 to 3; y is an integer from 1 to 4; R¹ is selectedfrom hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbonatoms and y bonding sites; R² is selected from aliphatic hydrocarbyleneradicals having from 2 to 4 carbon atoms; R³ is selected from hydrogen,and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6carbon atoms; at least one of R¹ and R³ is selected from saidhydrocarbon radicals; and wherein said polyoxyalkylene glycol ethershave a molecular weight of from about 100 to about 300 atomic massunits; ii) amides represented by the formulae R¹C(O)NR²R³ andcyclo-[R⁴CON(R⁵)—], wherein R¹, R², R³ and R⁵ are independently selectedfrom aliphatic and alicyclic hydrocarbon radicals having from 1 to 12carbon atoms, and at most one aromatic radical having from 6 to 12carbon atoms; R⁴ is selected from aliphatic hydrocarbylene radicalshaving from 3 to 12 carbon atoms; and wherein said amides have amolecular weight of from about 100 to about 300 atomic mass units; iii)ketones represented by the formula R¹C(O)R², wherein R¹ and R² areindependently selected from aliphatic, alicyclic and aryl hydrocarbonradicals having from 1 to 12 carbon atoms, and wherein said ketones havea molecular weight of from about 70 to about 300 atomic mass units; iv)nitriles represented by the formula R¹CN, wherein R¹ is selected fromaliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12carbon atoms, and wherein said nitriles have a molecular weight of fromabout 90 to about 200 atomic mass units; v) chlorocarbons represented bythe formula RCl_(x), wherein; x is 1 or 2; R is selected from aliphaticand alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; andwherein said chlorocarbons have a molecular weight of from about 100 toabout 200 atomic mass units; vi) aryl ethers represented by the formulaR¹OR², wherein: R¹ is selected from aryl hydrocarbon radicals havingfrom 6 to 12 carbon atoms; R² is selected from aliphatic hydrocarbonradicals having from 1 to 4 carbon atoms; and wherein said aryl ethershave a molecular weight of from about 100 to about 150 atomic massunits; vii) 1,1,1-trifluoroalkanes represented by the formula CF₃R¹,wherein R¹ is selected from aliphatic and alicyclic hydrocarbon radicalshaving from about 5 to about 15 carbon atoms; viii) fluoroethersrepresented by the formula R¹OCF₂CF₂H, wherein R¹ is selected fromaliphatic, alicyclic, and aromatic hydrocarbon radicals having fromabout 5 to about 15 carbon atoms; or wherein said fluoroethers arederived from fluoroolefins and polyols, wherein said fluoroolefins areof the type CF₂═CXY, wherein X is hydrogen, chlorine or fluorine, and Yis chlorine, fluorine, CF₃ or OR_(f), wherein R_(f) is CF₃, C₂F₅, orC₃F₇; and said polyols are linear or branched, wherein said linearpolyols are of the type HOCH₂(CHOH)_(x)(CRR′)_(y)CH₂OH, wherein R and R′are hydrogen, CH₃ or C₂H₅, x is an integer from 0-4, y is an integerfrom 0-3 and z is either zero or 1, and said branched polyols are of thetype C(OH)_(t)(R)_(u)(CH₂OH)_(v)[(CH₂)_(m)CH₂OH]_(w), wherein R may behydrogen, CH₃ or C₂H₅, m is an integer from 0 to 3, t and u are 0 or 1,v and w are integers from 0 to 4, and also wherein t+u+v+w=4; and ix)lactones represented by structures [B], [C], and [D]:

wherein, R₁ through R₈ are independently selected from hydrogen, linear,branched, cyclic, bicyclic, saturated and unsaturated hydrocarbylradicals; and the molecular weight is from about 100 to about 300 atomicmass units; and x) esters represented by the general formula R¹CO₂R²,wherein R¹ and R² are independently selected from linear and cyclic,saturated and unsaturated, alkyl and aryl radicals; and wherein saidesters have a molecular weight of from about 80 to about 550 atomic massunits.

The particular composition which includes a compatibilizer as describedabove, or which includes a dye as described above, or which includes adye and a solubilizing agent as described above may be used in a methodof producing cooling. The method of producing cooling comprisesevaporating this composition in the vicinity of a body to be cooled andthereafter condensing said composition. These particular compositionsmay also be used in a method of producing heat. The method of producingheat comprises condensing this composition in the vicinity of a body tobe heated and thereafter evaporating said composition.

In another particular embodiment, the present invention further relatesto a method of solubilizing a refrigerant or heat transfer fluidcomposition of the present invention in a refrigeration lubricantselected from the group consisting of mineral oils, alkylbenzenes,synthetic paraffins, synthetic napthenes, and poly(alpha)olefins,wherein said method comprises contacting said lubricant with saidrefrigerant or heat transfer fluid composition in the presence of aneffective amount of a compatibilizer, wherein said compatibilizer isselected from the group consisting of:

a) polyoxyalkylene glycol ethers represented by the formulaR¹[(OR²)_(x)OR³]_(y), wherein: x is an integer from 1 to 3; y is aninteger from 1 to 4; R¹ is selected from hydrogen and aliphatichydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R²is selected from aliphatic hydrocarbylene radicals having from 2 to 4carbon atoms; R³ is selected from hydrogen, and aliphatic and alicyclichydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R¹and R³ is selected from said hydrocarbon radicals; and wherein saidpolyoxyalkylene glycol ethers have a molecular weight of from about 100to about 300 atomic mass units; b) amides represented by the formulaeR¹C(O)NR²R³ and cyclo-[R⁴CON(R⁵)—], wherein R¹, R², R³ and R⁵ areindependently selected from aliphatic and alicyclic hydrocarbon radicalshaving from 1 to 12 carbon atoms, and at most one aromatic radicalhaving from 6 to 12 carbon atoms; R⁴ is selected from aliphatichydrocarbylene radicals having from 3 to 12 carbon atoms; and whereinsaid amides have a molecular weight of from about 100 to about 300atomic mass units; c) ketones represented by the formula R¹C(O)R²,wherein R¹ and R² are independently selected from aliphatic, alicyclicand aryl hydrocarbon radicals having from 1 to 12 carbon atoms, andwherein said ketones have a molecular weight of from about 70 to about300 atomic mass units; d) nitriles represented by the formula R¹CN,wherein R¹ is selected from aliphatic, alicyclic or aryl hydrocarbonradicals having from 5 to 12 carbon atoms, and wherein said nitrileshave a molecular weight of from about 90 to about 200 atomic mass units;e) chlorocarbons represented by the formula RCl_(x), wherein; x is 1 or2; R is selected from aliphatic and alicyclic hydrocarbon radicalshaving from 1 to 12 carbon atoms; and wherein said chlorocarbons have amolecular weight of from about 100 to about 200 atomic mass units; f)aryl ethers represented by the formula R¹OR², wherein: R¹ is selectedfrom aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R² isselected from aliphatic hydrocarbon radicals having from 1 to 4 carbonatoms; and wherein said aryl ethers have a molecular weight of fromabout 100 to about 150 atomic mass units; g) 1,1,1-trifluoroalkanesrepresented by the formula CF₃R′, wherein R¹ is selected from aliphaticand alicyclic hydrocarbon radicals having from about 5 to about 15carbon atoms; h) fluoroethers represented by the formula R¹OCF₂CF₂H,wherein R¹ is selected from aliphatic and alicyclic hydrocarbon radicalshaving from about 5 to about 15 carbon atoms; or wherein saidfluoroethers are derived from fluoro-olefins and polyols, wherein saidfluoro-olefins are of the type CF₂═CXY, wherein X is hydrogen, chlorineor fluorine, and Y is chlorine, fluorine, CF₃ or OR_(f), wherein R_(f)is CF₃, C₂F₅, or C₃F₇; and said polyols are of the typeHOCH₂CRR′(CH₂)_(z)(CHOH)_(x)CH₂(CH₂OH)_(y), wherein R and R′ arehydrogen, CH₃ or C₂H₅, x is an integer from 0-4, y is an integer from0-3 and z is either zero or 1; and i) lactones represented by structures[B], [C], and [D]:

wherein, R₁ through R₈ are independently selected from hydrogen, linear,branched, cyclic, bicyclic, saturated and unsaturated hydrocarbylradicals; and the molecular weight is from about 100 to about 300 atomicmass units; and j) esters represented by the general formula R¹CO₂R²,wherein R¹ and R² are independently selected from linear and cyclic,saturated and unsaturated, alkyl and aryl radicals; and wherein saidesters have a molecular weight of from about 80 to about 550 atomic massunits.

In a particular embodiment, the refrigerant or heat transfer fluidcomposition of the paragraph above is selected from the group consistingof: wherein said refrigerant or heat transfer fluid comprises acomposition selected from the group consisting of: about 1 weightpercent to about 99 weight percent HFC-1225ye and about 99 weightpercent to about 1 weight percent HFC-152a; about 1 weight percent toabout 99 weight percent HFC-1225ye and about 99 weight percent to about1 weight percent HFC-1234yf; about 1 weight percent to about 99 weightpercent HFC-1225ye and about 99 weight percent to about 1 weight percenttrans-HFC-1234ze; about 1 weight percent to about 99 weight percentHFC-1225ye and about 99 weight percent to about 1 weight percentHFC-1243zf; about 1 weight percent to about 99 weight percenttrans-HFC-1234ze and about 99 weight percent to about 1 weight percentHFC-134a; about 1 weight percent to about 99 weight percenttrans-HFC-1234ze and about 99 weight percent to about 1 weight percentHFC-152a; about 1 weight percent to about 99 weight percenttrans-HFC-1234ze and about 99 weight percent to about 1 weight percentHFC-227ea; and about 1 weight percent to about 99 weight percenttrans-HFC-1234ze and about 99 weight percent to about 1 weight percentCF₃I.

In another embodiment, the present invention relates to blowing agentcompositions comprising the fluoroolefin-containing compositions of thepresent invention as described herein for use in preparing foams. Inother embodiments the invention provides foamable compositions, andpreferably polyurethane and polyisocyanate foam compositions, and methodof preparing foams. In such foam embodiments, one or more of the presentfluoroolefin-containing compositions are included as a blowing agent infoamable compositions, which composition preferably includes one or moreadditional components capable of reacting and foaming under the properconditions to form a foam or cellular structure. Any of the methods wellknown in the art, such as those described in “Polyurethanes Chemistryand Technology,” Volumes I and II, Saunders and Frisch, 1962, John Wileyand Sons, New York, N.Y., which is incorporated herein by reference, maybe used or adapted for use in accordance with the foam embodiments ofthe present invention.

The present invention further relates to a method of forming a foamcomprising: (a) adding to a foamable composition afluoroolefin-containing composition of the present invention; and (b)reacting the foamable composition under conditions effective to form afoam.

Another embodiment of the present invention relates to the use of thefluoroolefin-containing compositions as described herein for use aspropellants in sprayable compositions. Additionally, the presentinvention relates to a sprayable composition comprising thefluoroolefin-containing compositions as described herein. The activeingredient to be sprayed together with inert ingredients, solvents andother materials may also be present in a sprayable composition.Preferably, the sprayable composition is an aerosol. Suitable activematerials to be sprayed include, without limitations, cosmeticmaterials, such as deodorants, perfumes, hair sprays, cleaners, andpolishing agents as well as medicinal materials such as anti-asthma andanti-halitosis medications.

The present invention further relates to a process for producing aerosolproducts comprising the step of adding a fluoroolefin-containingcomposition as described herein to active ingredients in an aerosolcontainer, wherein said composition functions as a propellant.

A further aspect provides methods of suppressing a flame, said methodscomprising contacting a flame with a fluid comprising afluoroolefin-containing composition of the present disclosure. Anysuitable methods for contacting the flame with the present compositionmay be used. For example, a fluoroolefin-containing composition of thepresent disclosure may be sprayed, poured, and the like onto the flame,or at least a portion of the flame may be immersed in the flamesuppression composition. In light of the teachings herein, those ofskill in the art will be readily able to adapt a variety of conventionalapparatus and methods of flame suppression for use in the presentdisclosure.

A further embodiment provides methods of extinguishing or suppressing afire in a total-flood application comprising providing an agentcomprising a fluoroolefin-containing composition of the presentdisclosure; disposing the agent in a pressurized discharge system; anddischarging the agent into an area to extinguish or suppress fires inthat area.

Another embodiment provides methods of inerting an area to prevent afire or explosion comprising providing an agent comprising afluoroolefin-containing composition of the present disclosure; disposingthe agent in a pressurized discharge system; and discharging the agentinto the area to prevent a fire or explosion from occurring.

The term “extinguishment” is usually used to denote complete eliminationof a fire; whereas, “suppression” is often used to denote reduction, butnot necessarily total elimination, of a fire or explosion. As usedherein, terms “extinguishment” and “suppression” will be usedinterchangeably. There are four general types of halocarbon fire andexplosion protection applications. (1) In total-flood fireextinguishment and/or suppression applications, the agent is dischargedinto a space to achieve a concentration sufficient to extinguish orsuppress an existing fire. Total flooding use includes protection ofenclosed, potentially occupied spaces such, as computer rooms as well asspecialized, often unoccupied spaces such as aircraft engine nacellesand engine compartments in vehicles. (2) In streaming applications, theagent is applied directly onto a fire or into the region of a fire. Thisis usually accomplished using manually operated wheeled or portableunits. A second method, included as a streaming application, uses a“localized” system, which discharges agent toward a fire from one ormore fixed nozzles. Localized systems may be activated either manuallyor automatically. (3) In explosion suppression, afluoroolefin-containing composition of the present disclosure isdischarged to suppress an explosion that has already been initiated. Theterm “suppression” is normally used in this application because theexplosion is usually self-limiting. However, the use of this term doesnot necessarily imply that the explosion is not extinguished by theagent. In this application, a detector is usually used to detect anexpanding fireball from an explosion, and the agent is dischargedrapidly to suppress the explosion. Explosion suppression is usedprimarily, but not solely, in defense applications. (4) In inertion, afluoroolefin-containing composition of the present disclosure isdischarged into a space to prevent an explosion or a fire from beinginitiated. Often, a system similar or identical to that used fortotal-flood fire extinguishment or suppression is used. Usually, thepresence of a dangerous condition (for example, dangerous concentrationsof flammable or explosive gases) is detected, and thefluoroolefin-containing composition of the present disclosure is thendischarged to prevent the explosion or fire from occurring until thecondition can be remedied.

The extinguishing method can be carried out by introducing thecomposition into an enclosed area surrounding a fire. Any of the knownmethods of introduction can be utilized provided that appropriatequantities of the composition are metered into the enclosed area atappropriate intervals. For example, a composition can be introduced bystreaming, e.g., using conventional portable (or fixed) fireextinguishing equipment; by misting; or by flooding, e.g., by releasing(using appropriate piping, valves, and controls) the composition into anenclosed area surrounding a fire. The composition can optionally becombined with an inert propellant, e.g., nitrogen, argon, decompositionproducts of glycidyl azide polymers or carbon dioxide, to increase therate of discharge of the composition from the streaming or floodingequipment utilized.

Preferably, the extinguishing process involves introducing afluoroolefin-containing composition of the present disclosure to a fireor flame in an amount sufficient to extinguish the fire or flame. Oneskilled in this field will recognize that the amount of flamesuppressant needed to extinguish a particular fire will depend upon thenature and extent of the hazard. When the flame suppressant is to beintroduced by flooding, cup burner test data is useful in determiningthe amount or concentration of flame suppressant required to extinguisha particular type and size of fire.

Laboratory tests useful for determining effective concentration rangesof fluoroolefin-containing compositions when used in conjunction withextinguishing or suppressing a fire in a total-flood application or fireinertion are described, for example, in U.S. Pat. No. 5,759,430.

EXAMPLES Example 1 Impact of Vapor Leakage

A vessel is charged with an initial composition at a temperature ofeither −25° C. or if specified, at 25° C., and the initial vaporpressure of the composition is measured. The composition is allowed toleak from the vessel, while the temperature is held constant, until 50weight percent of the initial composition is removed, at which time thevapor pressure of the composition remaining in the vessel is measured.Results are shown in Table 9.

TABLE 9 After After 50% 50% Composition Initial P Initial P Leak LeakDelta P wt % (Psia) (kPa) (Psia) (kPa) (%) HFC-1234yf/HFC-32  7.4/92.649.2 339 49.2 339 0.0%  1/99 49.2 339 49.2 339 0.0% 20/80 49.0 338 48.8337 0.3% 40/60 47.5 327 47.0 324 1.0% 57/43 44.9 309 40.5 280 9.6% 58/4244.6 308 40.1 276 10.2% HFC-1234yf/HFC-125 10.9/89.1 40.8 281 40.8 2810.0%  1/99 40.3 278 40.2 277 0.0% 20/80 40.5 279 40.3 278 0.4% 40/6038.7 267 37.0 255 4.4% 50/50 37.4 258 34.0 235 9.0% 51/49 37.3 257 33.7232 9.6% 52/48 37.1 256 33.3 229 10.3% HFC-1234yf/HFC-134  1/99 11.7 8111.6 80 0.7% 10/90 12.8 88 12.2 84 4.5% 20/80 13.7 95 13.0 89 5.6% 40/6015.2 105 14.6 101 4.1% 60/40 16.3 113 16.0 110 2.0% 80/20 17.2 119 17.1118 0.6% 90/10 17.6 121 17.5 121 0.2% 99/1  17.8 123 17.8 123 0.0%HFC-1234yf/HFC-134a 70.4/29.6 18.4 127 18.4 127 0.0% 80/20 18.3 126 18.3126 0.1% 90/10 18.2 125 18.1 125 0.1% 99/1  17.9 123 17.9 123 0.1% 40/6017.9 123 17.8 123 0.7% 20/80 17.0 117 16.7 115 1.7% 10/90 16.4 113 16.1111 1.5%  1/99 15.6 107 15.6 107 0.3% HFC-1234yf/HFC-152a 91.0/9.0  17.9123 17.9 123 0.0% 99/1  17.9 123 17.8 123 0.1% 60/40 17.4 120 17.2 1190.7% 40/60 16.6 115 16.4 113 1.6% 20/80 15.7 108 15.4 106 2.0% 10/9015.1 104 14.9 103 1.5%  1/99 14.6 100 14.5 100 0.2% HFC-1234yf/HFC-161 1/99 25.3 174 25.3 174 0.0% 10/90 25.2 174 25.2 174 0.1% 20/80 24.9 17224.8 171 0.8% 40/60 23.8 164 23.2 160 2.6% 60/40 22.0 152 21.3 147 3.2%80/20 19.8 137 19.5 134 1.9% 90/10 18.8 129 18.6 128 0.9% 99/1  17.9 12317.9 123 0.1% HFC-1234yf/FC-143a 17.3/82.7 39.5 272 39.5 272 0.0% 10/9039.3 271 39.3 271 0.1%  1/99 38.7 267 38.6 266 0.1% 40/60 38.5 266 37.8260 1.9% 60/40 36.3 250 32.8 226 9.5% 61/39 36.1 249 32.4 223 10.2%HFC-1234yf/HFC-227ea 84.6/15.4 18.0 124 18.0 124 0.0% 90/10 18.0 12418.0 124 0.0% 99/1  17.9 123 17.9 123 0.0% 60/40 17.6 121 17.4 120 1.2%40/60 16.7 115 15.8 109 5.4% 29/71 15.8 109 14.2 98 9.7% 28/72 15.7 10814.1 97 10.2% HFC-1234yf/HFC-236fa 99/1  17.8 122 17.7 122 0.2% 90/1017.0 117 16.6 115 2.4% 80/20 16.2 112 15.4 106 5.1% 70/30 15.3 106 14.097 8.5% 66/34 15.0 103 13.5 93 10.0% HFC-1234yf/HFC-1225ye  1/99 11.6 8011.5 79 0.5% 10/90 12.6 87 12.2 84 3.2% 20/80 13.5 93 12.9 89 4.3% 40/6015.0 103 14.4 99 3.7% 60/40 16.2 111 15.8 109 2.2% 80/20 17.1 118 16.9117 0.9% 90/10 17.5 120 17.4 120 0.3% 99/1  17.8 123 17.8 123 0.0%HFC-1234yf/trans-HFC-1234ze  1/99 11.3 78 11.3 78 0.4% 10/90 12.2 8411.8 81 3.3% 20/80 13.1 90 12.5 86 4.6% 40/60 14.6 101 14.0 96 4.3%60/40 15.8 109 15.4 106 2.7% 80/20 16.9 117 16.7 115 1.1% 90/10 17.4 12017.3 119 0.5% 99/1  17.8 123 17.8 123 0.1% HFC-1234yf/HFC-1243zf  1/9913.1 90 13.0 90 0.2% 10/90 13.7 94 13.5 93 1.6% 20/80 14.3 99 14.0 972.4% 40/60 15.5 107 15.1 104 2.2% 60/40 16.4 113 16.2 112 1.4% 80/2017.2 119 17.1 118 0.5% 90/10 17.5 121 17.5 121 0.2% 99/1  17.8 123 17.8123 0.0% HFC-1234yf/propane 51.5/48.5 33.5 231 33.5 231 0.0% 60/40 33.4230 33.3 229 0.4% 80/20 31.8 220 29.0 200 8.9% 81/19 31.7 218 28.5 19610.0% 40/60 33.3 230 33.1 228 0.6% 20/80 32.1 221 31.2 215 2.9% 10/9031.0 214 30.2 208 2.6%  1/99 29.6 204 29.5 203 0.4% HFC-1234yf/n-butane98.1/1.9  17.9 123 17.9 123 0.0% 99/1  17.9 123 17.9 123 0.0% 100/0 17.8 123 17.8 123 0.0% 80/20 16.9 116 16.1 111 4.4% 70/30 16.2 112 14.499 10.8% 71/29 16.3 112 14.6 101 9.9% HFC-1234yf/isobutane 88.1/11.919.0 131 19.0 131 0.0% 95/5  18.7 129 18.6 128 0.7% 99/1  18.1 125 18.0124 0.6% 60/40 17.9 123 16.0 110 10.3% 61/39 17.9 123 16.2 112 9.4%HFC-1234yf/DME 53.5/46.5 13.1 90 13.1 90 0.0% 40/60 13.3 92 13.2 91 0.7%20/80 14.1 97 13.9 96 1.3% 10/90 14.3 99 14.3 98 0.5%  1/99 14.5 10014.5 100 0.0% 80/20 14.5 100 14.0 96 3.3% 90/10 15.8 109 15.3 105 3.5%99/1  17.6 121 17.5 121 0.6% HFC-1234yf/CF₃SCF₃  1/99 12.1 83 12.0 830.2% 10/90 12.9 89 12.7 87 2.0% 20/80 13.8 95 13.4 92 2.8% 40/60 15.1104 14.7 101 2.7% 60/40 16.2 112 15.9 110 1.9% 80/20 17.1 118 16.9 1170.9% 90/10 17.5 120 17.4 120 0.5% 99/1  17.8 123 17.8 123 0.0%HFC-1234yf/CF₃I  1/99 12.0 83 12.0 83 0.2% 10/90 12.9 89 12.7 87 1.7%20/80 13.7 94 13.3 92 2.6% 40/60 15.1 104 14.7 101 2.7% 60/40 16.2 11115.8 109 2.0% 80/20 17.1 118 16.9 116 1.1% 90/10 17.5 120 17.4 120 0.5%99/1  17.8 123 17.8 123 0.1% HFC-125/HFC-1234yf/isobutane (25° C.)85.1/11.5/3.4 201.3 1388 201.3 1388 0.0% HFC-125/HFC-1234yf/n-butane(25° C.) 67/32/1 194.4 1340 190.2 1311 2.2% HFC-32/HFC-125/HFC-1234yf(25° C.) 40/50/10 240.6 1659 239.3 1650 0.5% 23/25/52 212.6 1466 192.91330 9.3% 15/45/40 213.2 1470 201.3 1388 5.6% 10/60/30 213.0 1469 206.01420 3.3% HFC-1225ye/trans-HFC-1234ze 63.0/37.0 11.7 81 11.7 81 0.0%80/20 11.6 80 11.6 80 0.0% 90/10 11.6 80 11.6 80 0.1% 99/1  11.5 79 11.579 0.0% 60/40 11.7 81 11.7 81 0.0% 40/60 11.6 80 11.6 80 0.1% 20/80 11.579 11.4 79 0.2% 10/90 11.3 78 11.3 78 0.1%  1/99 11.2 77 11.2 77 0.1%HFC-1225ye/HFC-1243zf 40.0/60.0 13.6 94 13.6 94 0.0% 20/80 13.4 93 13.492 0.1% 10/90 13.2 91 13.2 91 0.2%  1/99 13.0 90 13.0 90 0.0% 60/40 13.492 13.4 92 0.4% 80/20 12.8 88 12.6 87 1.4% 90/10 12.3 85 12.1 83 1.5%99/1  11.6 80 11.5 79 0.3% HFC-1225ye/HFC-134 52.2/47.8 12.8 88 12.8 880.0% 80/20 12.4 85 12.3 85 0.6% 90/10 12.0 83 11.9 82 0.8% 99/1  11.5 7911.5 79 0.2% 40/60 12.7 88 12.7 87 0.2% 20/80 12.3 85 12.2 84 0.8% 10/9012.0 83 11.9 82 0.9%  1/99 11.6 80 11.6 80 0.2% HFC-1225ye/HFC-134a 1/99 15.5 107 15.5 107 0.0% 10/90 15.2 105 15.2 105 0.3% 20/80 15.0 10314.9 103 0.5% 40/60 14.4 99 14.2 98 1.0% 60/40 13.6 94 13.4 93 1.4%80/20 12.7 88 12.5 86 1.6% 90/10 12.2 84 12.0 83 1.3% 99/1  11.5 80 11.579 0.2% HFC-1225ye/HFC-152a  7.3/92.7 14.5 100 14.5 100 0.0%  1/99 14.5100 14.5 100 0.0% 40/60 14.2 98 14.2 98 0.4% 60/40 13.7 95 13.6 93 1.1%80/20 12.9 89 12.7 87 1.5% 90/10 12.2 84 12.1 83 1.1% 99/1  11.5 80 11.579 0.1% HFC-1225ye/HFC-161  1/99 25.2 174 25.2 174 0.0% 10/90 24.9 17224.8 171 0.6% 20/80 24.5 169 24.0 165 2.0% 40/60 22.9 158 21.4 148 6.5%56/44 20.9 144 18.8 130 10.0% 99/1  11.7 81 11.6 80 1.0% 90/10 14.1 9713.0 90 7.5% 84/16 15.5 107 14.0 96 9.9% 83/17 15.8 109 14.2 98 10.2%HFC-1225ye/HFC-227ea  1/99 10.0 69 10.0 69 0.0% 10/90 10.1 70 10.1 700.2% 20/80 10.3 71 10.3 71 0.2% 40/60 10.6 73 10.6 73 0.4% 60/40 10.9 7510.9 75 0.4% 80/20 11.2 77 11.2 77 0.3% 90/10 11.3 78 11.3 78 0.1% 99/1 11.5 79 11.5 79 0.0% HFC-1225ye/HFC-236ea 99/1  11.4 79 11.4 79 0.0%90/10 11.3 78 11.2 77 0.5% 80/20 11.0 75 10.7 74 2.0% 60/40 10.2 70 9.465 8.3% 57/43 10.1 69 9.1 63 9.9% 56/44 10.0 69 9.0 62 10.6%HFC-1225ye/HFC-236fa 99/1  11.4 79 11.4 79 0.1% 90/10 11.1 77 11.0 761.1% 80/20 10.7 74 10.4 72 2.4% 60/40 9.8 68 9.2 63 6.6% 48/52 9.2 638.2 57 10.0% HFC-1225ye/HFC-245fa 99/1  11.4 79 11.4 78 0.3% 90/10 10.975 10.6 73 2.5% 80/20 10.4 72 9.8 68 5.7% 70/30 9.9 68 8.9 61 9.9% 69/219.8 68 8.8 60 10.5% HFC-1225ye/propane 29.7/70.3 30.4 209 30.4 209 0.0%20/80 30.3 209 30.2 208 0.2% 10/90 30.0 207 29.9 206 0.4%  1/99 29.5 20329.5 203 0.1% 60/40 29.5 203 28.5 197 3.3% 72/28 28.4 195 25.6 176 9.8%73/27 28.2 195 25.2 174 10.8% HFC-1225ye/n-butane 89.5/10.5 12.3 85 12.385 0.0% 99/1  11.7 81 11.6 80 0.9% 80/20 12.2 84 12.0 83 1.5% 65/35 11.780 10.5 72 9.9% 64/36 11.6 80 10.4 71 10.9% HFC-1225ye/isobutane79.3/20.7 13.9 96 13.9 96 0.0% 90/10 13.6 94 13.3 92 2.4% 99/1  11.9 8211.6 80 2.8% 60/40 13.5 93 13.0 89 4.1% 50/50 13.1 91 11.9 82 9.6% 49/5113.1 90 11.8 81 10.2% HFC-1225ye/DME 82.1/17.9 10.8 74 10.8 74 0.0%90/10 10.9 75 10.9 75 0.3% 99/1  11.4 78 11.4 78 0.2% 60/40 11.5 79 11.277 2.4% 40/60 12.8 88 12.1 84 4.8% 20/80 13.9 96 13.5 93 3.0% 10/90 14.398 14.1 97 1.1%  1/99 14.5 100 14.4 100 0.1% HFC-1225ye/CF₃I  1/99 11.982 11.9 82 0.0% 10/90 11.9 82 11.8 82 0.1% 20/80 11.8 81 11.8 81 0.0%40/60 11.7 80 11.7 80 0.0% 60/40 11.6 80 11.6 80 0.0% 80/20 11.5 79 11.579 0.0% 90/10 11.5 79 11.5 79 0.0% 99/1  11.5 79 11.5 79 0.0%HFC-1225ye/CF₃SCF₃ 37.0/63.0 12.4 86 12.4 86 0.0% 20/80 12.3 85 12.3 850.1% 10/90 12.2 84 12.2 84 0.1%  1/99 12.0 83 12.0 83 0.1% 60/40 12.3 8512.3 85 0.2% 80/20 12.0 83 11.9 82 0.4% 90/10 11.7 81 11.7 81 0.3% 99/1 11.5 79 11.5 79 0.1% HFC-1225ye/HFC-134a/HFC-152a (25° C.) 76/9/15 81.3561 80.5 555 1.0% HFC-1225ye/HFC-134a/HFC-161 (25° C.) 86/10/4 82.1 56680.2 553 2.3% HFC-1225ye/HFC-134a/isobutane (25° C.) 87/10/3 83.4 57580.3 554 3.7% HFC-1225ye/HFC-134a/DME (25° C.) 87/10/3 77.2 532 76.0 5241.6% HFC-1225ye/HFC-152a/isobutane (25° C.) 85/13/2 81.2 560 79.3 5472.3% HFC-1225ye/HFC-152a/DME (25° C.) 85/13/2 76.6 528 76.0 524 0.8%HFC-1225ye/HFC-1234yf/HFC-134a (25° C.) 70/20/10 86.0 593 84.0 579 2.3%20/70/10 98.2 677 97.5 672 0.7% HFC-1225ye/HFC-1234yf/HFC-152a (25° C.)70/25/5 85.1 587 83.4 575 2.0% 25/70/5 95.4 658 94.9 654 0.5%HFC-1225ye/HFC-1234yf/HFC-125 (25° C.) 25/71/4 105.8 729 96.3 664 9.0%75/21/4 89.5 617 83.0 572 7.3% 75/24/1 85.3 588 82.3 567 3.5% 25/74/198.0 676 95.1 656 3.0% HFC-1225ye/HFC-1234yf/CF₃I (25° C.) 40/40/20 87.5603 86.0 593 1.7% 45/45/10 89.1 614 87.7 605 1.6%HFC-1225ye/HFC-134a/HFC-152a/HFC-32 (25° C.) 74/8/17/1 86.1 594 81.5 5625.3% HFC-125/HFC-1225ye/isobutane (25° C.) 85.1/11.5/3.4 186.2 1284179.2 1236 3.8% HFC-32/HFC-125/HFC-1225ye (25° C.) 30/40/30 212.7 1467194.6 1342 8.5% trans-HFC-1234ze/cis-HFC-1234ze 99/1  11.1 77 11.1 760.4% 90/10 10.5 72 10.1 70 3.4% 80/20 9.8 68 9.1 63 7.1% 73/27 9.3 648.4 58 9.9% 72/28 9.3 64 8.3 57 10.3% trans-HFC-1234ze/HFC-1243zf17.0/83.0 13.0 90 13.0 90 0.0% 10/90 13.0 90 13.0 90 0.0%  1/99 13.0 9013.0 90 0.0% 40/60 12.9 89 12.9 89 0.1% 60/40 12.6 87 12.5 86 0.6% 80/2012.1 83 12.0 82 0.8% 90/10 11.7 80 11.6 80 0.7% 99/1  11.2 77 11.2 770.1% trans-HFC-1234ze/HFC-134 45.7/54.3 12.5 86 12.5 86 0.0% 60/40 12.485 12.4 85 0.2% 80/20 12.0 83 11.9 82 0.7% 90/10 11.7 80 11.6 80 0.7%99/1  11.2 77 11.2 77 0.1% 20/80 12.2 84 12.2 84 0.4% 10/90 11.9 82 11.982 0.6%  1/99 11.6 80 11.6 80 0.1% trans-HFC-1234ze/HFC-134a  9.5/90.515.5 107 15.5 107 0.0%  1/99 15.5 107 15.5 107 0.0% 40/60 15.1 104 15.0103 0.9% 60/40 14.3 99 14.0 96 2.5% 80/20 13.1 90 12.6 87 4.0% 90/1012.3 85 11.9 82 3.3% 99/1  11.3 78 11.3 78 0.5%trans-HFC-1234ze/HFC-152a 21.6/78.4 14.6 101 14.6 101 0.0% 10/90 14.6101 14.6 101 0.0%  1/99 14.5 100 14.5 100 0.0% 40/60 14.5 100 14.5 1000.1% 60/40 14.1 97 13.9 96 1.1% 80/20 13.2 91 12.8 88 2.5% 90/10 12.4 8512.0 83 2.6% 99/1  11.3 78 11.3 78 0.4% trans-HFC-1234ze/HFC-161  1/9925.2 174 25.2 174 0.0% 10/90 25.0 172 24.8 171 0.6% 20/80 24.5 169 24.0165 2.1% 40/60 22.8 157 21.2 146 7.0% 52/48 21.3 147 19.2 132 9.9% 53/4721.2 146 19.0 131 10.2% 99/1  11.5 79 11.3 78 1.2% 90/10 13.8 95 12.6 878.6% 88/12 14.3 99 12.9 89 9.5% 87/13 14.5 100 13.1 90 10.0%trans-HFC-1234ze/HFC-227ea 59.2/40.8 11.7 81 11.7 81 0.0% 40/60 11.6 8011.5 79 0.3% 20/80 11.1 76 10.9 75 1.3% 10/90 10.6 73 10.5 72 1.3%  1/9910.0 69 10.0 69 0.2% 80/20 11.6 80 11.5 80 0.2% 90/10 11.4 79 11.4 780.3% 99/1  11.2 77 11.2 77 0.0% trans-HFC-1234ze/HFC-236ea 99/1  11.2 7711.2 77 0.0% 90/10 11.0 76 11.0 76 0.4% 80/20 10.8 75 10.6 73 1.6% 60/4010.2 70 9.5 66 6.6% 54/46 9.9 69 9.0 62 9.5% 53/47 9.9 68 8.9 61 10.1%trans-HFC-1234ze/HFC-236fa 99/1  11.2 77 11.2 77 0.1% 90/10 10.9 75 10.875 0.8% 80/20 10.6 73 10.4 71 2.0% 60/40 9.8 67 9.3 64 5.4% 44/56 9.0 628.1 56 9.7% 43/57 8.9 62 8.0 55 10.1% trans-HFC-1234ze/HFC-245fa 99/1 11.2 77 11.1 77 0.2% 90/10 10.7 74 10.5 73 2.0% 80/20 10.3 71 9.8 684.7% 70/30 9.8 68 9.0 62 8.2% 67/33 9.7 67 8.7 60 9.7% 66/34 9.6 66 8.760 10.2% trans-HFC-1234ze/propane 28.5/71.5 30.3 209 30.3 209 0.0% 10/9030.0 206 29.9 206 0.3%  1/99 29.5 203 29.5 203 0.1% 40/60 30.2 208 30.1207 0.4% 60/40 29.3 202 28.3 195 3.4% 71/29 28.4 196 25.7 177 9.3% 72/2828.3 195 25.4 175 10.2% trans-HFC-1234ze/n-butane 88.6/11.4 11.9 82 11.982 0.0% 95/5  11.7 81 11.7 80 0.7% 99/1  11.4 78 11.3 78 0.6% 70/30 11.579 11.0 76 4.2% 62/38 11.2 77 10.2 70 9.3% 61/39 11.2 77 10.0 69 10.1%trans-HFC-1234ze/isobutane 77.9/22.1 12.9 89 12.9 89 0.0% 90/10 12.6 8712.4 85 1.6% 99/1  11.4 79 11.3 78 1.1% 60/40 12.6 87 12.3 85 2.4% 39/6111.7 81 10.6 73 9.8% 38/62 11.7 81 10.5 72 10.1% trans-HFC-1234ze/DME84.1/15.9 10.8 74 10.8 74 0.0% 90/10 10.8 75 10.8 75 0.0% 99/1  11.1 7711.1 77 0.0% 60/40 11.5 79 11.3 78 2.2% 40/60 12.7 88 12.2 84 4.4% 20/8013.9 96 13.5 93 2.9% 10/90 14.3 98 14.1 97 1.0%  1/99 14.5 100 14.5 1000.0% trans-HFC-1234ze/CF₃SCF₃ 34.3/65.7 12.7 87 12.7 87 0.0% 20/80 12.687 12.6 87 0.2% 10/90 12.4 85 12.3 85 0.3%  1/99 12.0 83 12.0 83 0.1%60/40 12.4 86 12.4 85 0.5% 80/20 12.0 82 11.8 81 1.1% 90/10 11.6 80 11.579 0.9% 99/1  11.2 77 11.2 77 0.2% trans-HFC-1234ze/CF₃I  1/99 11.9 8211.9 82 0.0% 10/90 11.9 82 11.9 82 0.0% 20/80 11.8 81 11.8 81 0.0% 40/6011.6 80 11.6 80 0.1% 60/40 11.4 79 11.4 79 0.1% 80/20 11.3 78 11.3 780.1% 90/10 11.3 78 11.2 77 0.1% 99/1  11.2 77 11.2 77 0.0%HFC-32/HFC-125/trans-HFC-1234ze (25° C.) 30/40/30 221.5 1527 209.4 14445.5% 30/50/20 227.5 1569 220.2 1518 3.2%HFC-125/trans-HFC-1234ze/n-butane (25° C.) 66/32/2 180.4 1244 170.3 11745.6% HFC-1243zf/HFC-134 63.0/37.0 13.5 93 13.5 93 0.0% 80/20 13.4 9313.4 92 0.1% 90/10 13.2 91 13.2 91 0.2% 99/1  13.0 90 13.0 90 0.0% 40/6013.3 92 13.3 91 0.5% 20/80 12.7 88 12.6 87 1.3% 10/90 12.3 84 12.1 831.5%  1/99 11.6 80 11.6 80 0.3% HFC-1243zf/HFC-134a 25.1/74.9 15.9 11015.9 110 0.0% 10/90 15.8 109 15.8 109 0.1%  1/99 15.5 107 15.5 107 0.1%40/60 15.8 109 15.8 109 0.2% 60/40 15.3 106 15.1 104 1.2% 80/20 14.4 9914.1 97 2.1% 90/10 13.8 95 13.5 93 1.7% 99/1  13.1 90 13.0 90 0.2%HFC-1243zf/HFC-152a 40.7/59.3 15.2 104 15.2 104 0.0% 20/80 15.0 103 15.0103 0.2% 10/90 14.8 102 14.7 102 0.3%  1/99 14.5 100 14.5 100 0.1% 60/4015.0 103 14.9 103 0.3% 80/20 14.4 99 14.2 98 1.1% 90/10 13.8 95 13.6 941.2% 99/1  13.1 90 13.1 90 0.2% HFC-1243zf/HFC-161  1/99 25.2 174 25.2174 0.0% 10/90 24.9 172 24.8 171 0.3% 20/80 24.5 169 24.2 167 0.9% 40/6023.3 160 22.6 156 2.9% 60/40 21.5 148 20.1 139 6.3% 78/22 18.8 130 16.9117 10.0% 90/10 16.2 111 14.6 101 9.5% 99/1  13.4 92 13.1 90 1.7%HFC-1243zf/HFC-227ea 78.5/21.5 13.1 90 13.1 90 0.0% 90/10 13.1 90 13.190 0.0% 99/1  13.0 90 13.0 90 0.0% 60/40 13.0 90 13.0 89 0.2% 40/60 12.687 12.5 86 1.1% 20/80 11.8 81 11.5 79 2.7% 10/90 11.1 76 10.7 74 2.8% 1/99 10.1 69 10.0 69 0.6% HFC-1243zf/HFC-236ea 99/1  13.0 89 13.0 890.0% 90/10 12.8 88 12.7 87 0.5% 80/20 12.5 86 12.3 84 1.8% 60/40 11.7 8111.0 76 6.6% 53/47 11.4 79 10.3 71 9.9% 52/48 11.4 78 10.2 70 10.5%HFC-1243zf/HFC-236fa 99/1  13.0 89 12.9 89 0.1% 90/10 12.6 87 12.5 861.0% 80/20 12.2 84 11.9 82 2.5% 60/40 11.3 78 10.5 73 6.6% 49/51 10.6 739.6 66 9.9% 48/52 10.6 73 9.5 65 10.2% HFC-1243zf/HFC-245fa 99/1  12.989 12.9 89 0.2% 90/10 12.5 86 12.2 84 2.1% 80/20 12.0 83 11.4 79 4.6%70/30 11.5 79 10.6 73 7.9% 66/34 11.3 78 10.2 70 9.6% 65/35 11.2 77 10.169 10.2% HFC-1243zf/propane 32.8/67.2 31.0 213 31.0 213 0.0% 10/90 30.3209 30.1 207 0.7%  1/99 29.5 204 29.5 203 0.1% 60/40 30.1 208 29.2 2013.2% 72/28 29.0 200 26.1 180 10.2% 71/29 29.2 201 26.5 182 9.3%HFC-1243zf/n-butane 90.3/9.7  13.5 93 13.5 93 0.0% 99/1  13.1 90 13.1 900.2% 62/38 12.6 87 11.4 79 9.4% 61/39 12.6 87 11.3 78 10.3%HFC-1243zf/isobutane 80.7/19.3 14.3 98 14.3 98 0.0% 90/10 14.1 97 14.096 0.9% 99/1  13.2 91 13.1 90 0.7% 60/40 13.8 95 13.4 92 3.2% 45/55 13.191 11.9 82 9.5% 44/56 13.1 90 11.8 81 10.1% HFC-1243zf/DME 72.7/27.312.0 83 12.0 83 0.0% 90/10 12.4 85 12.3 85 0.5% 99/1  12.9 89 12.9 890.1% 60/40 12.2 84 12.1 84 0.5% 40/60 13.0 90 12.7 88 2.2% 20/80 14.0 9613.7 95 2.0% 10/90 14.3 99 14.2 98 0.6%  1/99 14.5 100 14.5 100 0.0%cis-HFC-1234ze/HFC-236ea (25° C.) 20.9/79.1 30.3 209 30.3 209 0.0% 10/9030.2 208 30.2 208 0.0%  1/99 29.9 206 29.9 206 0.0% 40/60 30.0 207 30.0207 0.2% 60/40 29.2 201 28.9 199 0.9% 80/20 27.8 191 27.4 189 1.4% 90/1026.8 185 26.5 183 1.1% 99/1  25.9 178 25.8 178 0.2%cis-HFC-1234ze/HFC-236fa (25° C.)  1/99 39.3 271 39.3 271 0.0% 10/9038.6 266 38.4 265 0.3% 20/80 37.6 259 37.3 257 0.9% 40/60 35.4 244 34.5238 2.5% 60/40 32.8 226 31.4 216 4.3% 78/22 29.6 204 28.2 195 4.8% 90/1027.8 192 26.9 185 3.4% 99/1  26.0 179 25.8 178 0.5%cis-HFC-1234ze/HFC-245fa (25° C.) 76.2/23.7 26.2 180 26.2 180 0.0% 90/1026.0 179 26.0 179 0.0% 99/1  25.8 178 25.8 178 0.0% 60/40 26.0 179 25.9179 0.2% 40/60 25.3 174 25.0 173 0.9% 20/80 23.9 164 23.5 162 1.7% 10/9022.8 157 22.5 155 1.5%  1/99 21.6 149 21.5 149 0.2%cis-HFC-1234ze/n-butane 51.4/48.6 6.1 42 6.1 42 0.0% 80/20 5.8 40 5.2 369.3% 81/19 5.8 40 5.2 36 10.4% 40/60 6.1 42 6.0 41 0.7% 20/80 5.8 40 5.639 3.3% 10/90 5.6 38 5.4 37 3.1%  1/99 5.3 36 5.2 36 0.6%cis-HFC-1234ze/isobutane 26.2/73.8 8.7 60 8.7 60 0.0% 10/90 8.7 60 8.659 0.3%  1/99 8.5 59 8.5 59 0.0% 40/60 8.7 60 8.6 60 0.5% 60/40 8.4 588.0 55 4.3% 70/30 8.1 56 7.3 50 10.3% 69/31 8.2 56 7.4 51 9.4%cis-HFC-1234ze/2-methylbutane (25° C.) 86.6/13.4 27.3 188 27.3 188 0.0%90/10 27.2 187 27.2 187 0.1% 99/1  26.0 180 25.9 179 0.5% 60/40 25.8 17824.0 166 6.9% 55/45 25.3 174 22.8 157 10.0% cis-HFC-1234ze/n-pentane(25° C.) 92.9/9.1  26.2 181 26.2 181 0.0% 99/1  25.9 178 25.9 178 0.1%80/20 25.6 177 25.2 174 1.8% 70/30 24.8 171 23.5 162 5.6% 64/36 24.3 16722.0 152 9.2% 63/37 24.2 167 21.8 150 9.9% HFC-1234ye/HFC-134 (25° C.) 1/99 75.9 523 75.8 523 0.1% 10/90 73.8 509 73.0 503 1.1% 20/80 71.3 49169.0 476 3.1% 38/62 66.0 455 59.6 411 9.7% 39/61 65.7 453 58.9 406 10.2%HFC-1234ye/HFC-236ea (−25° C.) 24.0/76.0 3.4 23 3.4 23 0.0% 10/90 3.3 233.3 23 0.3%  1/99 3.3 23 3.3 23 0.0% 40/60 3.3 23 3.3 23 0.0% 60/40 3.222 3.2 22 0.9% 80/20 3.1 21 3.0 21 1.6% 90/10 2.9 20 2.9 20 1.4% 99/1 2.8 19 2.8 19 0.0% HFC-1234ye/HFC-236fa (25° C.)  1/99 39.2 270 39.2 2700.1% 10/90 37.7 260 37.3 257 1.1% 20/80 36.1 249 35.2 243 2.5% 40/6032.8 226 31.0 213 5.7% 60/40 29.3 202 26.7 184 8.8% 78/22 25.4 175 23.1159 9.1% 90/10 23.2 160 21.7 150 6.3% 99/1  21.0 145 20.8 144 0.8%HFC-1234ye/HFC-245fa (25° C.) 42.5/57.5 22.8 157 22.8 157 0.0% 20/8022.5 155 22.4 155 0.3% 10/90 22.1 152 22.0 152 0.3%  1/99 21.5 148 21.5148 0.0% 60/40 22.6 156 22.6 156 0.2% 80/20 22.0 152 21.9 151 0.6% 90/1021.5 148 21.3 147 0.6% 99/1  20.8 144 20.8 143 0.1%HFC-1234ye/cis-HFC-1234ze (25° C.)  1/99 25.7 177 25.7 177 0.0% 10/9025.6 176 25.6 176 0.0% 20/80 25.3 175 25.3 174 0.1% 40/60 24.7 170 24.5169 0.5% 60/40 23.7 163 23.5 162 1.0% 78/22 22.4 155 22.2 153 1.2% 90/1021.7 149 21.5 148 0.9% 99/1  20.9 144 20.8 144 0.1% HFC-1234ye/n-butane(25° C.) 41.2/58.8 38.0 262 38.0 262 0.0% 20/80 37.3 257 37.0 255 0.8%10/90 36.4 251 36.1 249 0.9%  1/99 35.4 244 35.3 243 0.2% 60/40 37.4 25836.9 254 1.4% 70/30 36.5 252 34.9 241 4.4% 78/22 35.3 243 31.8 219 9.9%79/21 35.1 242 31.3 216 10.9% HFC-1234ye/cyclopentane (25° C.) 99/1 20.7 143 20.7 143 0.0% 90/10 20.3 140 20.0 138 1.0% 80/20 19.5 134 18.7129 4.1% 70/30 18.6 128 16.9 116 9.5% 69/31 18.5 128 16.6 115 10.3%HFC-1234ye/isobutane (25° C.) 16.4/83.6 50.9 351 50.9 351 0.0% 10/9050.9 351 50.9 351 0.0%  1/99 50.5 348 50.5 348 0.0% 40/60 50.1 345 49.6342 1.0% 60/40 47.8 330 45.4 313 5.2% 68/32 46.4 320 42.0 289 9.5% 69/3146.2 318 41.4 286 10.3% HFC-1234ye/2-methylbutane (25° C.) 80.3/19.723.1 159 23.1 159 0.0% 90/10 22.8 157 22.6 156 1.1% 99/1  21.2 146 20.9144 1.0% 60/40 22.5 155 21.7 149 3.6% 47/53 21.5 148 19.4 134 9.6% 46/5421.4 148 19.2 133 10.1% HFC-1234ye/n-pentane (25° C.) 87.7/12.3 21.8 15021.8 150 0.0% 95/5  21.5 149 21.4 148 0.5% 99/1  21.0 145 20.9 144 0.4%60/40 20.5 141 18.9 131 7.7% 57/43 20.3 140 18.3 126 9.7% 56/44 20.2 13918.1 125 10.4%

The difference in vapor pressure between the original composition andthe composition remaining after 50 weight percent is removed is lessthen about 10 percent for compositions of the present invention. Thisindicates that the compositions of the present invention would beazeotropic or near-azeotropic.

Example 2 Refrigeration Performance Data

Table 10 shows the performance of various refrigerant compositions ofthe present invention as compared to HFC-134a. In Table 10, Evap Pres isevaporator pressure, Cond Pres is condenser pressure, Comp Disch T iscompressor discharge temperature, COP is energy efficiency, and CAP iscapacity. The data are based on the following conditions.

Evaporator temperature  40.0° F. (4.4° C.) Condenser temperature 130.0°F. (54.4° C.) Subcool amount  10.0° F. (5.5° C.) Return gas temperature 60.0° F. (15.6° C.) Compressor efficiency is 100%Note that the superheat is included in cooling capacity.

TABLE 10 Evap Evap Cond Cond Comp Comp Cap Composition Pres Pres PresPres Disch T Disch T (Btu/ Cap (wt %) (Psia) (kPa) (Psia) (kPa) (F.)(C.) min) (kW) COP HFC-134a 50.3 346 214 1476 156 68.9 213 3.73 4.41HFC-1225ye 37.6 259 165 1138 146 63.3 162 2.84 4.41 HFC-1225ye/HFC-152a(85/15) 39.8 274 173 1193 151 66.1 173 3.03 4.45 HFC-1225ye/HFC-32 46.5321 197 1358 151 66.1 200 3.50 4.53 (95/5) HFC-1225ye/HFC-32 (96/4) 44.2305 189 1303 150 65.6 191 3.35 4.51 HFC-1225ye/HFC-32 43.1 297 184 1269149 65.0 186 3.26 4.50 (97/3) HFC-1225ye/HFC-32 (94/6) 47.3 326 200 1379153 67.2 203 3.56 4.52 HFC-1225ye/HFC-32 (93/7) 48.8 336 205 1413 15467.8 210 3.68 4.53 HFC-1225ye/HFC-32 (90/10) 53.0 365 222 1531 157 69.4227 3.98 4.52 HFC-1225ye/HFC-134a 39.5 272 172 1186 147 63.9 169 2.964.40 (90/10) HFC-1225ye/CO₂ 43.2 298 179 1234 146 63.3 177 3.10 4.63(99/1) HFC-1225ye/HFC-134a/HFC-32 44.5 307 190 1310 150 65.6 191 3.354.49 (88/9/3) HFC-1225ye/HFC-134a/HFC-32 45.5 314 194 1338 151 66.1 1953.42 4.49 (88/8/4) HFC-1225ye/HFC-134a/HFC- 41.0 283 178 1227 153 67.2178 3.12 4.44 152a (76/9/15) HFC-1225ye/HFC-134a/HFC- 42.0 290 181 1248150 65.6 179 3.13 4.42 161 (86/10/4) HFC-1225ye/HFC-134a/propane 47.0324 195 1345 148 64.4 197 3.45 4.49 (87/10/3)HFC-1225ye/HFC-134a/i-butane 41.7 288 178 1227 146 63.3 175 3.06 4.39(87/10/3) HFC-1225ye/HFC-134a/DME 38.7 267 169 1165 149 65.0 168 2.944.44 (87/10/3) HFC-1225ye/HFC-134a/CO₂ 42.4 292 180 1241 147 63.9 1823.18 4.51 (88.5/11/.5) HFC-1225ye/HFC-134/HFC-32 43.0 296 185 1276 15065.6 187 3.27 4.51 (88/9/3) HFC-1225ye/HFC-152a/HFC-32 46.7 322 198 1365155 68.3 203 3.55 4.53 (85/10/5) HFC-1225ye/HFC-152a/HFC-32 45.5 314 1931331 155 68.3 198 3.47 4.52 (81/15/4) HFC-1225ye/HFC-152a/HFC-32 44.1304 188 1296 155 68.3 192 3.36 4.50 (82/15/3)HFC-1225ye/HFC-152a/propane 44.4 306 185 1276 151 66.1 190 3.33 4.52(85/13/2) HFC-1225ye/HFC-152a/i-butane 40.9 282 176 1214 150 65.6 1753.06 4.44 (85/13/2) HFC-1225ye/HFC-152a/DME 39.0 269 170 1172 152 66.7171 3.00 4.46 (85/13/2) HFC-1225ye/HFC-152a/CO₂ 44.8 309 185 1276 15166.1 195 3.42 4.64 (84/15/1) HFC-1225ye/HFC-152a/CO₂ 42.3 292 179 1234151 66.1 184 3.22 4.55 (84/15.5/0.5) HFC-1225ye/HFC-152a/CF₃I 42.0 290180 1241 155 68.3 181 3.17 4.46 (70/20/10) HFC-1234yf/HFC-32 58.6 404230 1586 149 65.0 228 4.00 4.36 (95/5) HFC-1234yf/HFC-134a 52.7 363 2101448 145 62.8 206 3.61 4.33 (90/10) HFC-1234yf/HFC-152a 53.5 369 2131468 150 65.6 213 3.73 4.38 (80/20) trans-HFC-1234ze/HFC-32 42.6 294 1831262 153 67.2 186 3.26 4.51 (95/5) trans-HFC-1234ze/HFC-32/CF₃I 43.5 300182 1255 154 67.8 184 3.22 4.46 (70/2/28) trans-HFC-1234ze/HFC-134a 38.1263 166 1145 149 65.0 165 2.89 4.44 (90/10) trans-HFC-1234ze/HFC-152a41.0 284 176 1214 154 67.8 177 3.10 4.48 (80/20)trans-HFC-1234ze/HFC-125 38.6 266 167 1151 148 64.4 167 2.92 4.45 (96/4)HFC-1225ye/HFC-1234yf 46.0 317 190 1310 145 62.8 186 3.26 4.35 (51/49)HFC-1225ye/HFC-1234yf 44.0 303 187 1289 146 63.3 179 3.13 4.30 (60/40)HFC-1225ye/HFC-1234yf/HFC- 43.0 296 183 1261 147 63.9 179 3.13 4.38 134a(70/20/10) HFC-1225ye/HFC-1234yf/HFC- 50.7 350 205 1412 145 62.8 2003.50 4.34 134a (20/70/10) HFC-1225ye/HFC-1234yf/HFC- 53.0 365 212 1464146 63.3 210 3.68 4.37 32 (25/73/2) HFC-1225ye/HFC-1234yf/HFC- 45.3 312190 1312 148 64.4 189 3.31 4.43 32 (75/23/2) HFC-1225ye/HFC-1234yf/HFC-47.6 328 200 1379 151 66.1 203 3.56 4.50 32 (85/10/5)HFC-1225ye/HFC-1234yf/HFC- 46.7 322 197 1358 151 66.1 200 3.50 4.51 32(90/5/5) HFC-1225ye/HFC-1234yf/HFC- 42.8 295 181 1250 147 63.9 179 3.134.40 152a (70/25/5) HFC-1225ye/HFC-1234yf/HFC- 49.9 344 202 1392 14663.3 199 3.49 4.35 152a (25/70/5) HFC-1225ye/HFC-1234yf/HFC- 51.6 356207 1429 145 62.8 202 3.54 4.33 125 (25/71/4) HFC-1225ye/HFC-1234yf/HFC-43.4 299 184 1268 146 63.3 180 3.15 4.38 125 (75/21/4)HFC-1225ye/HFC-1234yf/HFC- 42.4 292 180 1241 145 62.8 176 3.08 4.39 125(75/24/1) HFC-1225ye/HFC-1234yf/HFC- 50.2 346 202 1395 144 62.2 198 3.474.33 125 (25/74/1) HFC-1225ye/HFC-1234yf 49.8 343 201 1383 144 62.2 1963.43 4.34 (25/75) HFC-1225ye/HFC-1234yf/CF₃I 47.9 330 195.0 1344 147.564.2 192 3.36 4.34 (40/40/20) HFC-1225ye/HFC-1234yf/CF₃I 47.0 324 192.91330 146 63.3 189 3.31 4.35 (45/45/10) HFC-1225ye/HFC-1234yf/HFC- 49.5341 202.5 1396 146.9 63.8 201 3.52 4.4 32 (49/49/2)HFC-1225ye/HFC-134a/HFC- 42.5 293 183 1260 154 67.8 184.3 3.23 4.47152a/HFC-32 (74/8/17/1) HFC-1225ye/HFC-134a/HFC-32 47.5 328 201 1386 15266.7 204 3.57 4.49 (87/8/5) HFC-1225ye/HFC-1234yf/HFC- 48.1 332 198 1365145 62.8 193 3.38 4.35 125 (48/48/4) HFC-1225ye/HFC-1234yf/HFC- 50.5 348205 1413 148 64.4 204 3.57 4.39 32/CF₃I (45/44/2/9)HFC-1225ye/HFC-1234yf/HFC- 50.1 345 204 1407 148 64.4 202 3.54 4.3932/CF3I (47/46/2/5) HFC-1225ye/HFC-32/HFC-125 43.2 298 192 1324 151 66.1181 3.17 4.28 (94/2/4) HFC-1234yf/HFC-32/CF₃I 58.2 401 224 1544 152 66.7225 3.94 4.37 (60/2/38) HFC-1234yf/HFC-32/CF₃I 56.2 387 217 1496 15166.1 217 3.80 4.35 (60/1/39)) HFC-1234yf/CF₃I (60/40) 54.1 373 210 1448149 65.0 209 3.66 4.34 comparative? HFC-1234yf/HFC-125/CF₃I 56.8 392 2201517 147 63.9 217 3.80 4.31 (70/4/26) HFC-1234yf/HFC-125/CF₃I 56.4 389219 1510 146 63.3 215 3.77 4.32 (80/4/16) HFC-1234yf/HFC-125 (96/4) 55.1380 217 1496 144 62.2 212 3.71 4.31 HFC-1234yf/HFC-134a/CF₃I 54.7 377215 1482 148 64.4 211 3.70 4.32 (70/10/20) HFC-1234yf/HFC-152a/CF₃I 55.1380 214 1475 154 67.8 216 3.78 4.36 (50/10/40)

Several compositions have even higher energy efficiency (COP) thanHFC-134a while maintaining lower discharge pressures and temperatures.Capacity for the compositions listed in Table 10 is also similar toR134a indicating these compositions could be replacement refrigerantsfor R134a in refrigeration and air-conditioning, and in mobileair-conditioning applications in particular. Results also show coolingcapacity of HFC-1225ye can be improved with addition of other compoundssuch as HFC-32, HFC-134a, CO2 or HFC-1234yf. Those compositionscontaining hydrocarbon may also improve oil solubility with conventionalmineral oil and alkyl benzene lubricants.

Example 3 Refrigeration Performance Data

Table 11 shows the performance of various refrigerant compositions ofthe present invention as compared to R404A and R422A. In Table 11, EvapPres is evaporator pressure, Cond Pres is condenser pressure, Comp DischT is compressor discharge temperature, EER is energy efficiency, and CAPis capacity. The data are based on the following conditions.

Evaporator temperature −17.8° C.   Condenser temperature 46.1° C.Subcool amount  5.5° C. Return gas temperature 15.6° C. Compressorefficiency is 70%Note that the superheat is included in cooling capacity.

TABLE 11 Evap Cond P Compr Press Press Disch T CAP wt % (kPa)) (kPa)(C.) (kJ/m3) EER Existing Refrigerant Product R22 267 1774 144 1697 4.99R404A 330 2103 101.1 1769 4.64 R507A 342 2151 100.3 1801 4.61 R422A 3242124 95.0 1699 4.54 Candidate Replacement HFC-125/HFC- 85.1/11.5/3.4 3302137 93.3 1699 4.50 1225ye/isobutane HFC-125/trans-HFC- 86.1/11.5/2.4319 2096 94.4 1669 4.52 1234ze/isobutane HFC-125/HFC- 87.1/11.5/1.4 3432186 93.3 1758 4.52 1234yf/isobutane HFC-125/HFC- 85.1/11.5/3.4 322 210693.5 1674 4.52 1225ye/n-butane HFC-125/trans-HFC- 86.1/11.5/2.4 314 208394.8 1653 4.53 1234ze/n-butane HFC-125/HFC- 87.1/11.5/1.4 340 2173 93.41748 4.53 1234yf/n-butane HFC-32/HFC- 10/10/′80 173 1435 107 1159 4.97125/HFC-1225ye HFC-32/HFC- 25/25/50 276 2041 120 1689 4.73125/HFC-1225ye HFC-32/HFC- 25/40/35 314 2217 119 1840 4.66125/HFC-1225ye HFC-32/HFC- 30/10/60 265 1990 125 1664 4.78125/HFC-1225ye HFC-32/HFC- 30/15/55 276 2046 125 1710 4.76125/HFC-1225ye HFC-32/HFC- 30/20/50 287 2102 124 1757 4.73125/HFC-1225ye HFC-32/HFC- 30/30/40 311 2218 124 1855 4.68125/HFC-1225ye HFC-32/HFC- 30/35/35 324 2271 123 1906 4.66125/HFC-1225ye HFC-32/HFC- 35/15/50 296 2157 129 1820 4.72125/HFC-1225ye HFC-32/HFC- 35/20/45 308 2212 129 1868 4.70125/HFC-1225ye HFC-32/HFC- 35/30/35 332 2321 127 1968 4.66125/HFC-1225ye HFC-32/HFC- 35/40/25 357 2424 126 2068 4.64125/HFC-1225ye HFC-32/HFC- 50/30/20 390 2584 138 2277 4.54125/HFC-1225ye HFC-32/HFC- 40/30/30 353 2418 131 2077 4.66125/HFC-1225ye HFC-32/HFC- 40/35/25 364 2465 131 2124 4.64125/HFC-1225ye HFC-32/HFC- 45/30/25 372 2505 135 2180 4.66125/HFC-1225ye HFC-32/HFC- 10/20/10/60 190 1517 110 1255 4.97125/HFC-152a/HFC- 1225ye HFC-32/HFC- 15/25/10/50 221 1709 115 1422 4.90125/HFC-152a/HFC- 1225ye HFC-32/HFC- 20/20/15/45 229 1755 121 1485 4.90125/HFC-152a/HFC- 1225ye HFC-32/CF₃I/HFC- 30/20/50 272 1984 130 17064.80 1225ye HFC-32/CF₃I/HFC- 40/10/50 299 2159 137 1860 4.73 1225yeHFC-32/CF₃I/HFC- 30/30/40 286 2030 133 1774 4.80 1225ye HFC-32/CF₃I/HFC-30/60/10 314 2120 144 1911 4.75 1225ye HFC-32/CF₃I/HFC- 40/20/40 3152214 139 1936 4.73 1225ye HFC-32/CF₃I//HFC- 30/50/20 309 2101 139 18854.78 1225ye HFC-32/CF₃I/HFC- 40/40/20 346 2309 145 2079 4.71 1225yeHFC-32/CF₃I/HFC- 45/45/10 373 2432 152 2217 4.67 1225ye HFC-32/CF₃I/HFC-45/10/45 319 2260 141 1964 4.71 1225ye HFC-32/CF₃I/HFC- 50/10/40 3382353 145 2065 4.68 1225ye HFC-32/CF₃I/HFC- 50/20/30 356 2410 147 21504.68 1225ye HFC-32/CF₃I/HFC- 25/5/70 230 1781 122 1495 4.90 1225yeHFC-32/CF₃I/HFC- 60/30/10 409 2626 158 2434 4.66 1225ye HFC-32/CF₃I/HFC-50/25/25 364 2437 149 2192 4.68 1225ye HFC-32/CF₃I/HFC- 50/20/30 3562410 147 2156 4.68 1225ye HFC-32/CF₃I/HFC- 25/50/25 284 1964 134 17544.85 1225ye HFC-32/CF₃I/HFC- 45/30/25 353 2368 146 2124 4.71 1225yeHFC-32/CF₃I/HFC- 5/50/45 199 1377 107 1254 5.11 1234yf HFC-32/CF₃I/HFC-5/30/65 197 1382 103 1241 5.11 1234yf HFC-32/CF₃I/HFC- 10/25/65 220 1542107 1374 5.04 1234yf HFC-32/CF₃I/HFC- 20/10/70 255 1786 114 1577 4.951234yf HFC-32/CF₃I/HFC- 30/10/60 295 2020 123 1795 4.88 1234yfHFC-32/CF₃I/HFC- 30/20/50 305 2057 125 1843 4.85 1234yf HFC-32/CF₃I/HFC-30/30/40 314 2091 128 1887 4.85 1234yf HFC-32/CF₃I/HFC- 20/40/40 2751861 121 1679 4.92 1234yf HFC-32/CF₃I/HFC- 10/40/50 225 1558 111 14045.04 1234yf HFC-32/CF₃I/HFC- 50/20/30 378 2447 143 2238 4.73 1234yfHFC-32/CF₃I/HFC- 40/30/30 354 2305 137 2099 4.76 1234yf HFC-32/CF₃I/HFC-40/40/20 360 2336 142 2136 4.74 1234yf HFC-32/CF₃I/HFC- 35/35/30 3382217 135 2015 4.78 1234yf HFC-32/CF₃I/HFC- 35/30/35 334 2202 133 19964.80 1234yf HFC-32/CF₃I/HFC- 50/25/25 384 2468 145 2267 4.72 1234yfHFC-32/CF₃I/HFC- 40/20/20/20 331 2246 136 1999 4.76 1225ye/HFC-1234yfHFC-32/CF₃I/HFC- 30/20/25/25 290 2029 127 1782 4.83 1225ye/HFC-1234yfHFC-32/CF₃I/HFC- 30/10/30/30 279 1987 125 1728 4.83 1225ye/HFC-1234yfHFC-32/HFC- 25/25/25/25 297 2089 118 1772 4.76 125/HFC-1234yf/HFC-1225ye HFC-32/HFC- 20/30/25/25 286 2025 113 1702 4.64125/HFC- 1234yf/HFC-1225ye HFC-32/HFC- 20/30/30/20 290 2033 113 17174.76 125/HFC- 1234yf/HFC-1225ye HFC-32/HFC- 20/30/40/10 297 2048 1121746 4.78 125/HFC- 1234yf/HFC-1225ye HFC-32/HFC- 30/30/20/20 328 2251122 1925 4.71 125/HFC- 1234yf/HFC-1225ye HFC-32/HFC- 30/30/1/39 312 2217123 1858 4.68 125/HFC- 1234yf/HFC-1225ye HFC-32/HFC- 30/30/39/1 342 2275120 1979 4.73 125/HFC- 1234yf/HFC-1225ye HFC-32/HFC- 30/30/10/30 3202235 123 1891 4.68 125/HFC- 1234yf/HFC-1225ye HFC-32/HFC- 35/30/5/30 3372330 127 1986 4.66 125/HFC- 1234yf/HFC-1225ye HFC-32/HFC- 20/15/10/55240 1818 115 1513 4.85 125/HFC- 1234yf/HFC-1225ye HFC-32/HFC-30/15/10/45 284 2066 124 1743 4.76 125/HFC- 1234yf/HFC-1225yeHFC-32/HFC- 40/30/15/15 341 2364 132 2022 4.66 125/HFC-1234yf/HFC-1225ye HFC-32/HFC- 30/25/5/35/5 335 2240 121 1954 4.76125/CF₃I/HFC- 1234yf/HFC-1225ye HFC-32/HFC- 30/25/5/40 338 2245 121 19664.76 125/CF₃I/HFC-1234yf HFC-32/HFC- 25/35/35/5 323 2195 115 1837 4.64125/HFC- 1225ye/isobutane HFC-32/HFC- 25/38/35/2 318 2214 117 1837 4.64125/HFC- 1225ye/isobutane HFC-32/HFC- 25/38/35/2 330 2297 118 1892 4.59125/HFC- 1225ye/propane HFC-32/CF₃I/HFC- 50/20/25/5 321 2252 150 20104.76 1225ye/DME HFC-32/HFC- 35/30/30/5 293 2135 131 1823 4.76 125/HFC-1225ye/DME HFC-32/HFC- 35/33/30/2 320 2268 129 1925 4.68 125/HFC-1225ye/DME HFC-32/HFC- 35/35/28/2 324 2288 129 1943 4.68 125/HFC-1225ye/DME HFC-32/HFC- 25/50/25 365 2376 115 2040 4.66 125/HFC-1234yfHFC-32/HFC- 30/30/40 343 2276 120 1982 4.73 125/HFC-1234yf HFC-32/HFC-20/30/50 303 2059 112 1770 4.78 125/HFC-1234yf HFC-32/HFC- 25/25/10/40323 2154 118 1884 4.78 125/CF₃I/HFC-1234yf HFC-32/HFC- 25/25/10/40 2912088 121 1757 4.73 125/CF₃I/HFC- 1225ye HFC-32/HFC- 20/30/10/40 279 2017117 1680 4.73 125/CF₃I/HFC- 1225ye HFC-32/HFC- 20/35/5/40 285 2056 1161699 4.71 125/CF₃I/HFC- 1225ye HFC-32/HFC-1225ye 20/80 200 1620 117 13314.91 HFC-32/HFC-1225ye 30/70 246 1879 126 1587 4.85 HFC-32/HFC-1225ye40/60 284 2101 134 1788 4.74 HFC-32/HFC- 40/50/10 299 2159 137 1860 4.741225ye/CF₃I HFC-32/HFC- 50/40/10 337 2353 145 2065 4.69 1225ye/CF₃IHFC-32/HFC- 30/20/50 242 1854 128 1578 4.88 134a/HFC-1225ye FC-32/HFC-40/10/50 281 2078 135 1783 4.78 134a/HFC-1225ye FC-32/HFC- 40/20/40 2772053 136 1775 4.81 134a/HFC-1225ye FC-32/HFC- 40/30/30 274 2029 137 17624.85 134a/HFC-1225ye FC-32/HFC- 40/40/20 269 2004 138 1747 4.86134a/HFC-1225ye FC-32/HFC- 50/30/20 302 2189 145 1929 4.79134a/HFC-1225ye HFC-32/HFC- 40/30/20/10 287 2081 139 1828 4.88 134a/HFC-1225ye/CF₃I HFC-32/HFC- 40/30/15/15 294 2106 140 1862 4.81 134a/HFC-1225ye/CF₃I HFC-32/HFC- 30/30/30/10 254 1891 130 1637 4.88 134a/HFC-1225ye/CF₃I HFC-32/HFC- 30/10/30/15/15 280 2016 131 1756 4.83125/HFC-134a/HFC- 1225ye/CF₃I HFC-32/HFC- 30/10/20/20/20 291 2064 1311802 4.81 125/HFC-134a/HFC- 1225ye/CF₃I HFC-32/HFC- 30/30/20/20 253 1877127 1628 4.91 134a/HFC- 1225ye/HFC-1234yf HFC-32/HFC- 30/30/10/30 2591892 126 1651 4.90 134a/HFC- 1225ye/HFC-1234yf HFC-32/HFC- 35/25/5/35280 2003 129 1762 4.87 134a/HFC- 1225ye/HFC-1234yf HFC-32/HFC-35/20/10/30/5 286 2032 130 1790 4.85 134a/HFC- 1225ye/HFC- 1234yf/CF₃IHFC-32/HFC- 35/20/35/10 296 2063 130 1834 4.85 134a/HFC- 1234yf/CF₃IHFC-32/HFC- 35/10/45/10 306 2095 128 1868 4.84 134a/HFC- 1234yf/CF₃IHFC-32/HFC- 25/15/50/10 267 1878 121 1660 4.91 134a/HFC- 1234yf/CF₃IHFC-32/HFC- 30/30/30/10 272 1939 128 1712 4.88 134a/HFC- 1234yf/CF₃IHFC-32/HFC- 30/20/40/10 280 1968 126 1744 4.88 134a/HFC- 1234yf/CF₃IHFC-32/HFC- 30/20/30/20 289 2003 129 1787 4.87 134a/HFC- 1234yf/CF₃IHFC-32/HFC- 30/20/20/30 297 2035 132 1831 4.87 134a/HFC- 1234yf/CF₃IHFC-32/HFC- 25/20/25/30 279 1928 127 1729 4.89 134a/HFC- 1234yf/CF₃IHFC-32/HFC- 40/20/20/20 320 2188 138 1967 4.81 134a/HFC- 1234yf/CF₃IHFC-32/HFC- 50/10/20/20 362 2396 145 2183 4.74 134a/HFC- 1234yf/CF₃IHFC-32/HFC- 50/10/30/10 351 2354 141 2127 4.76 134a/HFC- 1234yf/CF₃IHFC-32/NH₃/HFC- 15/15/70 266 2004 152 1831 5.01 1225ye HFC-32/NH₃/HFC-20/20/60 289 2141 165 2008 5.00 1225ye HFC-32/NH₃/HFC- 20/10/70 265 2002144 1789 4.96 1225ye HFC-32/NH₃/HFC- 25/25/50 302 2229 178 2118 5.001225ye HFC-32/NH₃/HFC- 25/15/60 295 2171 158 2001 4.95 1225yeHFC-32/NH₃/HFC- 30/10/60 297 2182 151 1968 4.89 1225ye HFC-32/NH₃/HFC-25/25/40/10 305 2246 182 2138 5.00 1225ye/CF₃I HFC-32/NH₃/HFC-20/20/50/10 296 2162 168 2048 5.00 1225ye/CF₃I HFC-32/NH₃/HFC-15/15/55/15 278 2041 156 1899 5.00 1225ye/CF₃I HFC-32/NH₃/HFC-20/10/55/15 280 2052 148 1868 4.95 1225ye/CF₃I HFC-32/NH₃/HFC-20/10/50/20 311 2125 143 2005 4.99 1234yf/CF₃I HFC-32/NH₃/HFC-10/10/20/60 280 1928 152 1857 5.05 1234yf/CF₃I HFC-1225ye/R717 95/5 1591317 113 1121 5.16 HFC-1225ye/R717 90/10 194 1550 128 1368 5.14HFC-1225ye/R717 85/15 217 1698 141 1535 5.11 HFC-1225ye/R717 80/20 2431725 146 1750 5.43 HFC-125/HFC- 5/85/10 205 1613 127 1423 5.111225ye/R717 HFC-125/HFC- 10/80/10 212 1651 127 1455 5.09 1225ye/R717HFC-125/HFC- 15/75/10 220 1687 127 1486 5.04 1225ye/R717 HFC-125/HFC-20/70/10 227 1723 126 1516 5.02 1225ye/R717 HFC-125/HFC- 25/65/10 2351757 126 1547 5.00 1225ye/R717 HFC-125/HFC- 20/65/15 248 1845 138 16745.04 1225ye/R717 HFC-125/HFC- 20/75/5 195 1525 112 1291 5.02 1225ye/R717R32/HFC-125/HFC- 25/10/60/5 273 2029 135 1766 4.88 1225ye/R717R32/HFC-125/HFC- 20/20/55/5 273 2011 130 1740 4.85 1225ye/R717R32/HFC-125/HFC- 10/20/65/5 235 1787 121 1526 4.92 1225ye/R717R32/HFC-125/HFC- 25/10/55/10 295 2148 146 1936 4.90 1225ye/R717R32/HFC-125/HFC- 20/20/50/10 295 2125 142 1911 4.90 1225ye/R717R32/HFC-125/HFC- 10/20/60/10 262 1938 134 1722 4.95 1225ye/R717R32/HFC-125/HFC- 10/10/65/15 265 1974 147 1804 5.02 1225ye/R717R32/HFC-125/HFC- 10/20/55/15 278 2028 146 1859 5.00 1225ye/R717R32/HFC-125/HFC- 5/25/55/15 270 1967 141 1798 5.00 1225ye/R717R32/HFC-125/HFC- 10/20/60/10 295 2025 129 1865 5.00 1234yf/R717R32/HFC-125/HFC- 5/25/60/10 285 1958 125 1797 5.00 1234yf/R717

Several compositions have energy efficiency (EER) comparable top R404Aand R422A. Discharge temperatures are also lower than R404A and R507A.Capacity for the compositions listed in Table 11 is also similar toR404A, R507A, and R422A indicating these compositions could bereplacement refrigerants for R404A, R507A, or R422A in refrigeration andair-conditioning. Those compositions containing hydrocarbon may alsoimprove oil solubility with conventional mineral oil and alkyl benzenelubricants.

Example 4 Refrigeration Performance Data

Table 12 shows the performance of various refrigerant compositions ofthe present invention as compared to HCFC-22, R410A, R407C, and R417A.In Table 12, Evap Pres is evaporator pressure, Cond Pres is condenserpressure, Comp Disch T is compressor discharge temperature, EER isenergy efficiency, and CAP is capacity. The data are based on thefollowing conditions.

Evaporator temperature  4.4° C. Condenser temperature 54.4° C. Subcoolamount  5.5° C. Return gas temperature 15.6° C. Compressor efficiency is100%Note that the superheat is included in cooling capacity.

TABLE 12 Evap Cond Compr Press Press Disch T CAP wt % (kPa)) (kPa) (C.)(kJ/m³) EER Existing Refrigerant Product R22 573 2149 88.6 3494 14.73R410A 911 3343 89.1 4787 13.07 R407C 567 2309 80.0 3397 14.06 R417A 4941979 67.8 2768 13.78 Candidate Replacement HFC-32/HFC-125/HFC-1225ye30/40/30 732 2823 81.1 3937 13.20 HFC-32/HFC-125/HFC-1225ye 23/25/52 5982429 78.0 3409 13.54 HFC-32/HFC-125/trans-HFC- 30/50/20 749 2865 81.73975 13.10 1234ze HFC-32/HFC-125/trans-HFC- 23/25/52 546 2252 78.9 322213.80 1234ze HFC-32/HFC-125/HFC-1234yf 40/50/10 868 3185 84.4 4496 13.06HFC-32/HFC-125/HFC-1234yf 23/25/52 656 2517 76.7 3587 13.62HFC-32/HFC-125/HFC-1234yf 15/45/40 669 2537 73.3 3494 13.28HFC-32/HFC-125/HFC-1234yf 10/60/30 689 2586 71.3 3447 12.96HFC-125/HFC-1225ye/n-butane 65/32/3 563 2213 66.1 2701 12.87HFC-125/trans-HFC-1234ze/n- 66/32/2 532 2130 67.2 2794 13.08 butaneHFC-125/HFC-1234yf/n-butane 67/32/1 623 2344 66.1 3043 12.85HFC-125/HFC-1225ye/isobutane 65/32/3 574 2244 66.2 2874 12.79HFC-125/trans-HFC- 66/32/2 538 2146 67.4 2808 13.04 1234ze/isobutaneHFC-125/HFC-1234yf/isobutane 67/32/1 626 2352 66.3 3051 12.83

Compositions have energy efficiency (EER) comparable to R22, R407C,R417A, and R410A while maintaining low discharge temperatures. Capacityfor the compositions listed in Table 12 is also similar to R22, R407Cand R417A indicating these compositions could be replacementrefrigerants for R22, R407C or R417A in refrigeration andair-conditioning. Those compositions containing hydrocarbon may alsoimprove oil solubility with conventional mineral oil and alkyl benzenelubricant.

Example 5 Refrigeration Performance Data

Table 13 shows the performance of various refrigerant compositions ofthe present invention as compared to HCFC-22 and R410A. In Table 13,Evap Pres is evaporator pressure, Cond Pres is condenser pressure, CompDisch T is compressor discharge temperature, EER is energy efficiency,and CAP is capacity. The data are based on the following conditions.

Evaporator temperature  4° C. Condenser temperature 43° C. Subcoolamount  6° C. Return gas temperature 18° C. Compressor efficiency is 70%Note that the superheat is included in cooling capacity.

TABLE 13 Compr Evap Cond Disch Press Press Temp (kPa) (kPa) (C.) CAP(kJ/m3) EER Existing refrigerant product R22 565 1648 90.9 3808 9.97R410A 900 2571 88.1 5488 9.27 Candidate replacement product (Compositionwt %) HFC-32/HFC-1225ye (40/60) 630 1948 86.7 4242 9.56HFC-32/HFC-1225ye (45/55) 666 2041 88.9 4445 9.49 HFC-32/HFC-1225ye(50/50) 701 2127 91.0 4640 9.45 HFC-32/HFC-1225ye/CF₃I (40/30/20) 7112104 90.6 4605 9.56 HFC-32/HFC-1225ye/CF₃I (45/30/25) 737 2176 92.2 47659.45 HFC-32/HFC-1225ye/CF₃I (45/35/20) 724 2151 91.4 4702 9.45HFC-32/HFC-134a/HFC-1225ye 607 1880 87.8 4171 9.69 (40/30/30)HFC-32/HFC-134a/HFC-1225ye 637 1958 89.9 4347 9.66 (45/30/25)HFC-32/HFC-134a/HFC-1225ye 631 1944 90.2 4326 9.69 (45/35/20)HFC-32/HFC-134a/HFC-1234yf/CF₃I 611 1845 89.6 4107 9.66 (30/20/5/45)HFC-32/HFC-134a/HFC-1234yf/CF₃I 575 1745 86.5 3891 9.76 (25/20/10/45)HFC-32/HFC-134a/HFC-1234yf/CF₃I 646 1939 91.2 4308 9.62 (35/10/5/40)HFC-32/HFC-134a/HFC-1225ye/HFC- 587 1822 84 4001 9.69 1234yf(34/12/47/7) HFC-32/HFC-134a/HFC-1225ye/HFC- 561 1752 81.9 3841 9.731234yf (30/8/52/10) HFC-32/HFC-134a/HFC-1225ye/HFC- 597 1852 84.3 40519.66 1234yf (35/6/52/7) HFC-32/HFC-1225ye (40/60) 630 1948 86.7 42429.56 HFC-32/HFC-1225ye (45/55) 666 2041 88.9 4445 9.49 HFC-32/HFC-1225ye(50/50) 701 2127 91.0 4640 9.45 HFC-32/HFC-1225ye (55/45) 734 2206 93.04825 9.45 HFC-32/HFC-1225ye (60/40) 764 2280 94.9 5001 9.42HFC-32/HFC-1225ye/CF₃I (65/30/5) 808 2376 97.5 5237 9.42HFC-32/HFC-1225ye/CF₃I (65/17.5/17.5) 845 2445 99.4 5408 9.39HFC-32/HFC-1225ye/CF₃I (65/5/30) 879 2508 101.7 5565 9.49HFC-32/HFC-1225ye/CF₃I(60/30/10) 795 2337 96.3 5140 9.42HFC-32/HFC-1225ye/CF₃I (60/20/20) 857 2319 92.5 5565 10.27HFC-32/HFC-1225ye/CF₃I (60/10/30) 852 2442 99.5 5404 9.39HFC-32/HFC-1225ye/CF₃I (55/40/5) 749 2235 93.6 4894 9.42HFC-32/HFC-1225ye/CF₃I (55/25/20) 793 2319 95.7 5098 9.42HFC-32/HFC-1225ye/CF₃I (55/20/25) 808 2345 96.5 5163 9.42HFC-32/HFC-1225ye/CF₃I (55/5/40) 844 2413 99.4 5332 9.39HFC-32/HFC-1225ye/CF₃I (50/45/5) 819 2350 98.3 5176 9.39HFC-32/HFC-1225ye/CF₃I (50/25/25) 774 2264 94.4 4970 9.42HFC-32/HFC-1225ye/CF₃I (50/5/45) 716 2156 91.6 4706 9.45HFC-32/HFC-1225ye/CF₃I (45/50/5) 680 2069 89.5 4509 9.49HFC-32/HFC-1225ye/CF₃I (45/30/25) 737 2176 92.2 4765 9.45HFC-32/HFC-1225ye/CF₃I (45/35/20) 724 2151 91.4 4702 9.45HFC-32/HFC-1225ye/CF₃I (45/25/30) 750 2200 93.0 4825 9.45HFC-32/HFC-1225ye/CF₃I (45/5/50) 789 2276 97.3 4996 9.39HFC-32/HFC-1225ye/CF₃I (40/50/10) 657 2003 87.9 4365 9.52HFC-32/HFC-1225ye/CF₃I (40/30/30) 711 2104 90.6 4605 9.56HFC-32/HFC-1225ye/CF₃I (40/10/50) 749 2178 94.7 4775 9.42HFC-32/HFC-1234yf/CF₃I (60/30/10) 823 2372 93.9 5228 9.45HFC-32/HFC-1234yf/CF₃I (60/20/20) 844 2415 96.0 5335 9.45HFC-32/HFC-1234yf/CF₃I (60/10/30) 862 2459 98.5 5433 9.49HFC-32/HFC-1234yf/CF₃I (55/35/10) 798 2305 91.7 5069 9.49HFC-32/HFC-1234yf/CF₃I (55/5/40) 850 2419 98.9 5347 9.39HFC-32/HFC-1234yf/CF₃I (50/40/10) 769 2232 89.4 4899 9.52HFC-32/HFC-1234yf/CF₃I (50/30/20) 790 2275 91.3 5002 9.49HFC-32/HFC-1234yf/CF₃I (50/20/30) 808 2313 93.4 5095 9.45HFC-32/HFC-1234yf/CF₃I (50/10/40) 821 2345 96.2 5168 9.42HFC-32/HFC-1234yf/CF₃I (50/5/45) 825 2357 97.8 5192 9.39HFC-32/HFC-1234yf/CF₃I (45/10/45) 792 2274 95.0 4999 9.42HFC-32/HFC-1234yf/CF₃I (45/5/50) 794 2283 96.8 5011 9.39HFC-32/HFC-1234yf/CF₃I (40/50/10) 705 2067 85.0 4523 9.59HFC-32/HFC-1234yf/CF₃I (40/40/20) 725 2108 86.5 4622 9.56HFC-32/HFC-1234yf/CF₃I (40/10/50) 759 2192 93.8 4806 9.42HFC-32/HFC-1234yf/CF₃I (40/5/55) 759 2197 95.7 4808 9.39HFC-32/HFC-134a/HFC-1225ye 713 2156 96.2 4807 9.56 (60/30/10)HFC-32/HFC-134a/HFC-1225ye 730 2196 95.8 4875 9.52 (60/20/20)HFC-32/HFC-134a/HFC-1225ye 747 2237 95.3 4941 9.49 (60/10/30)HFC-32/HFC-134a/HFC-1225ye 727 2187 93.1 4802 9.49 (55/5/40)HFC-32/HFC-134a/HFC-1225ye 704 2131 93.7 4723 9.56 (55/20/25)HFC-32/HFC-134a/HFC-1225ye 674 2060 94.7 4605 9.62 (55/40/5)HFC-32/HFC-134a/HFC-1225ye 695 2110 91.1 4623 9.49 (50/5/45)HFC-32/HFC-134a/HFC-1225ye 671 2045 91.9 4536 9.62 (50/25/25)HFC-32/HFC-134a/HFC-1225ye 645 1982 92.8 4433 9.69 (50/45/5)HFC-32/HFC-134a/HFC-1225ye 662 2027 89.0 4433 9.52 (45/5/50)HFC-32/HFC-134a/HFC-1225ye 642 1971 89.7 4367 9.66 (45/25/30)HFC-32/HFC-134a/HFC-1225ye 637 1958 89.9 4347 9.66 (45/30/25)HFC-32/HFC-134a/HFC-1225ye 631 1944 90.2 4326 9.69 (45/35/20)HFC-32/HFC-134a/HFC-1225ye 615 1903 90.9 4259 9.73 (45/50/5)HFC-32/HFC-134a/HFC-1225ye 623 1926 87.0 4224 9.62 (40/10/50)HFC-32/HFC-134a/HFC-1225ye 607 1880 87.8 4171 9.69 (40/30/30)HFC-32/HFC-134a/HFC-1225ye 589 1833 88.7 4101 9.76 (40/50/10)HFC-32/HFC-125/HFC-1225ye (60/5/35) 784 2323 94.6 5087 9.42HFC-32/HFC-125/HFC-1225ye 803 2365 94.2 5173 9.42 (60/10/30)HFC-32/HFC-125/HFC-1225ye 822 2407 93.9 5256 9.39 (60/15/25)HFC-32/HFC-125/HFC-1225ye 742 2220 90.3 4820 9.42 (50/10/40)HFC-32/HFC-125/HFC-1225ye (50/5/45) 721 2173 90.7 4730 9.45HFC-32/HFC-125/HFC-1225ye 762 2266 90.0 4911 9.42 (50/15/35)HFC-32/HFC-125/HFC-1225ye 692 2097 85.9 4518 9.45 (40/15/45)HFC-32/HFC-125/HFC-1225ye 671 2047 86.2 4425 9.49 (40/10/50)HFC-32/HFC-125/HFC-1225ye 654 2001 83.8 4304 9.49 (35/15/50)HFC-32/HFC-134a/HFC-1234yf/CF₃I 611 1845 89.6 4107 9.66 (30/20/5/45)HFC-32/HFC-134a/HFC-1234yf/CF₃I 575 1745 86.5 3891 9.76 (25/20/10/45)HFC-32/HFC-134a/HFC-1234yf/CF₃I 646 1939 91.2 4308 9.62 (35/10/5/40)HFC-32/HFC-134a/HFC-1225ye/HFC- 587 1822 84.0 4001 9.69 1234yf(34/12/47/7) HFC-32/HFC-134a/HFC-1225ye/HFC- 561 1752 81.9 3841 9.731234yf (30/8/52/10) HFC-32/HFC-134a/HFC-1225ye/HFC- 597 1852 84.3 40519.66 1234yf (35/6/52/7) HFC-32/HFC-1225ye/HFC-1234yf/CF₃I 862 2470 98.95470 9.42 (65/5/10/20) HFC-32/HFC-1225ye/HFC-1234yf/CF₃I 818 2389 96.75270 9.42 (65/20/10/5) HFC-32/HFC-1225ye/HFC-1234yf/CF₃I 857 2465 99.35456 9.39 (65/10/5/20) HFC-32/HFC-1225ye/HFC-1234yf/CF₃I 828 2401 95.95298 9.45 (65/10/20/5) HFC-32/HFC-1225ye/HFC-1234yf/CF₃I 785 2316 95.25090 9.42 (60/30/5/5) HFC-32/HFC-1225ye/HFC-1234yf/CF₃I 809 2345 93.35163 9.45 (60/5/30/5) HFC-32/HFC-1225ye/HFC-1234yf/CF₃I 860 2448 99.05419 9.39 (60/5/5/30) HFC-32/HFC-1225ye/HFC-1234yf/CF₃I 835 2405 96.85309 9.42 (60/10/10/20) HFC-32/HFC-1225ye/HFC-1234yf/CF₃I 818 2358 95.65197 9.42 (55/10/10/25) HFC-32/HFC-1225ye/HFC-1234yf/CF₃I 839 2399 97.85298 9.42 (55/5/5/35) HFC-32/HFC-1225ye/HFC-1234yf/CF₃I 770 2263 92.14966 9.45 (55/20/20/5) HFC-32/HFC-1225ye/HFC-1234yf/CF₃I 783 2278 91.15005 9.49 (55/5/35/5) HFC-32/HFC-1225ye/HFC-1234yf/CF₃I 755 2243 93.24912 9.45 (55/35/5/5) HFC-32/HFC-1225ye/HFC-1234yf/CF₃I 816 2339 96.75153 9.42 (50/5/5/40) HFC-32/HFC-1225ye/HFC-1234yf/CF₃I 798 2303 94.35067 9.45 (50/10/10/20) HFC-32/HFC-1225ye/HFC-1234yf/CF₃I 752 2213 90.74848 9.49 (50/20/20/10) HFC-32/HFC-1225ye/HFC-1234yf/CF₃I 744 2161 91.64743 9.45 (40/10/10/40) HFC-32/HFC-1225ye/HFC-1234yf/CF₃I 728 2127 89.44663 9.52 (40/15/15/30) HFC-32/HFC-1225ye/HFC-1234yf/CF₃I 707 2087 87.74566 9.52 (40/20/20/20) HFC-32/HFC-125/HFC-1225ye/CF₃I 865 2481 97.05453 9.35 (60/10/10/20) HFC-32/HFC-125/HFC-1225ye/CF₃I 873 2488 99.15494 9.39 (60/5/5/30) HFC-32/HFC-125/HFC-1225ye/CF₃I 799 2352 95.2 51599.42 (60/5/30/5) HFC-32/HFC-125/HFC-1225ye/CF₃I 845 2437 97.4 5367 9.39(60/5/15/20) HFC-32/HFC-125/HFC-1225ye/CF₃I 847 2414 95.2 5288 9.39(50/10/5/35) HFC-32/HFC-125/HFC-1225ye/CF₃I 758 2250 90.9 4891 9.42(50/10/35/5) HFC-32/HFC-125/HFC-1225ye/CF₃I 834 2384 96.7 5238 9.39(50/5/5/40) HFC-32/HFC-125/HFC-1225ye/CF₃I 797 2315 93.9 5070 9.42(50/5/20/25) HFC-32/HFC-125/HFC-1225ye/CF₃I 857 2440 93.9 5327 9.39(50/15/5/30) HFC-32/HFC-125/HFC-1225ye/CF₃I 779 2297 90.5 4983 9.39(50/15/30/5) HFC-32/HFC-125/HFC-1234yf/CF₃I 875 2494 96.1 5481 9.39(60/10/10/20) HFC-32/HFC-125/HFC-1234yf/CF₃I 879 2494 98.6 5508 9.39(60/5/5/30) HFC-32/HFC-125/HFC-1234yf/CF₃I 860 2455 96.0 5410 9.42(60/5/15/20) HFC-32/HFC-125/HFC-1234yf/CF₃I 852 2421 94.7 5304 9.39(50/10/5/35) HFC-32/HFC-125/HFC-1234yf/CF₃I 840 2391 96.2 5254 9.39(50/5/5/40) HFC-32/HFC-125/HFC-1234yf/CF₃I 818 2340 92.3 5134 9.45(50/5/20/25) HFC-32/HFC-125/HFC-1234yf/CF₃I 862 2447 93.4 5343 9.39(50/15/5/30) HFC-32/HFC-125/HFC-1225/HFC- 759 2232 89.8 4873 9.491234yf/CF₃I (50/5/20/20/5) HFC-32/HFC-125/HFC-1225/HFC- 829 2370 95.25206 9.42 1234yf/CF₃I (50/5/5/5/35) HFC-32/HFC-125/HFC-1225/HFC- 7752272 89.8 4948 9.45 1234yf/CF₃I (50/10/20/15/5)HFC-32/HFC-125/HFC-1225/HFC- 839 2397 93.8 5248 9.39 1234yf/CF₃I(50/10/5/5/30) HFC1225ye/R717 445 1433 82.2 3306 10.17 HFC1225ye/R717493 1569 89.0 3666 10.17 HFC1225ye/R717 525 1660 95.0 3921 10.17HFC1225ye/R717 370 1217 74.1 2767 10.20 HFC-32/HFC-1225ye/R717 594 185595.0 4312 10.00 HFC-32/HFC-1225ye/R717 594 1855 91.2 4232 9.90HFC-32/HFC-1225ye/R717 542 1718 84.7 3846 9.86 HFC-32/HFC-1225ye/R717(10/85/5) 462 1494 79.9 3361 10.00 HFC-125/HFC-1225ye/R717 (5/80/15) 5131622 88.7 3778 10.14 HFC-125/HFC-1225ye/R717 (10/75/15) 526 1652 88.43834 10.10 HFC-125/HFC-1225ye/R717 533 1666 88.3 3861 10.07(12.5/72.5/15) HFC-125/HFC-1225ye/R717 (15/70/15) 539 1680 88.1 388810.07 HFC-125/HFC-1225ye/R717 (20/75/5) 444 1411 77.8 3142 10.00HFC-125/HFC-1225ye/R717 (10/85/5) 410 1327 74.0 2984 10.10HFC-32/R125/HFC-1225ye/R717 573 1776 90.1 4104 10.03 (5/15/65/15)HFC-32/R125/HFC-1225ye/R717 591 1822 92.9 4242 10.03 (5/17.5/60/17.5)HFC-32/R125/HFC-1225ye/R717 604 1861 92.1 4299 9.97 (10/15/60/15)HFC-32/R125/HFC-1225ye/R717 625 1926 90.5 4370 9.83 (20/10/60/10)HFC-32/R125/HFC-1225ye/R717 616 1905 86.3 4224 9.73 (25/10/60/5)HFC-32/R125/HFC-1225ye/R717 579 1806 84.1 4009 9.76 (20/10/65/5)HFC-32/R125/HFC-1225ye/R717 596 1845 83.9 4079 9.73 (20/15/60/5)Compositions have energy efficiency (EER) comparable to R22 and R410Awhile maintaining reasonable discharge temperatures. Capacity forcertain compositions listed in Table 13 is also similar to R22indicating these compositions could be replacement refrigerants for R22in refrigeration and air-conditioning. Additionally, there arecompositions listed in Table 13 with capacity approaching or equivalentto that for R410A indicating that those compositions could bereplacement refrigerants for R410A in refrigeration andair-conditioning.

Example 6 Flammability

Flammable compounds may be identified by testing under ASTM (AmericanSociety of Testing and Materials) E681-01, with an electronic ignitionsource. Such tests of flammability were conducted on HFC-1234yf,HFC-1225ye and mixtures of the present disclosure at 101 kPa (14.7psia), 100° C. (212° F.), and 50 percent relative humidity, at variousconcentrations in air in order to determine the lower flammability limit(LFL) and upper flammability limit (UFL). The results are given in Table13.

TABLE 14 Composition LFL (vol % in air) UFL (vol % in air) HFC-1225yeNon-flammable Non-flammable (100 wt %) HFC-1234yf 5.0 14.5 (100 wt %)HFC- 8.5 12.0 1234yf/1225ye (50/50 wt %) HFC- Non-flammableNon-flammable 1234yf/1225ye (40/60 wt %) HFC- 13.0  17.0 1225ye/HFC- 32(60/40 wt %) HFC- Non-flammable Non-flammable 1225ye/HFC- 32 (65/35 wt%)

The results indicate that while HFC-1234yf is flammable, addition ofHFC-1225ye reduces the flammability. Therefore, compositions comprisingabout 1 weight percent to about 49 weight percent HFC-1234yf and about99 weight percent to about 51 weight percent HFC-1225ye are preferred.Results also show HFC-1225ye reduces the flammability of HFC-32 andresults in a non-flammable composition at 65/35 wt % HFC-1225ye/HFC-32.

What is claimed is:
 1. A composition comprising HFC-1234yf and n-butanewherein the HFC-1234yf and n-butane in said composition are present asan azeotropic or near-azeotropic component that comprises from about 71to 99 weight percent HFC-1234yf and from about 29 to 1 weight percentn-butane.
 2. The composition of claim 1, further comprising a lubricantselected from the group consisting of polyol esters, polyalkyleneglycols, polyvinyl ethers, mineral oil, alkylbenzenes, syntheticparaffins, synthetic napthenes, and poly(alpha)olefins.
 3. Thecomposition of claim 2, further comprising a compatibilizer selectedfrom the group consisting of: a) polyoxyalkylene glycol ethersrepresented by the formula R¹[(OR²)_(x)OR³]_(y), wherein: x is aninteger from 1 to 3; y is an integer from 1 to 4; R¹ is selected fromhydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atomsand y bonding sites; R² is selected from aliphatic hydrocarbyleneradicals having from 2 to 4 carbon atoms; R³ is selected from hydrogen,and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6carbon atoms; at least one of R¹ and R³ is selected from saidhydrocarbon radicals; and wherein said polyoxyalkylene glycol ethershave a molecular weight of from about 100 to about 300 atomic massunits; b) amides represented by the formulae R¹C(O)NR²R³ and cyclo-[R⁴CON(R⁵)], wherein R¹, R², R³ and R⁵ are independently selected fromaliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbonatoms, and at most one aromatic radical having from 6 to 12 carbonatoms; R⁴ is selected from aliphatic hydrocarbylene radicals having from3 to 12 carbon atoms; and wherein said amides have a molecular weight offrom about 100 to about 300 atomic mass units; c) ketones represented bythe formula R¹C(O)R², wherein R¹ and R² are independently selected fromaliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12carbon atoms, and wherein said ketones have a molecular weight of fromabout 70 to about 300 atomic mass units; d) nitriles represented by theformula R¹CN, wherein R¹ is selected from aliphatic, alicyclic or arylhydrocarbon radicals having from 5 to 12 carbon atoms, and wherein saidnitriles have a molecular weight of from about 90 to about 200 atomicmass units; e) chlorocarbons represented by the formula RCI_(x),wherein; x is 1 or 2; R is selected from aliphatic and alicyclichydrocarbon radicals having from 1 to 12 carbon atoms; and wherein saidchlorocarbons have a molecular weight of from about 100 to about 200atomic mass units; f) aryl ethers represented by the formula R¹OR²,wherein: R¹ is selected from aryl hydrocarbon radicals having from 6 to12 carbon atoms; R² is selected from aliphatic hydrocarbon radicalshaving from 1 to 4 carbon atoms; and wherein said aryl ethers have amolecular weight of from about 100 to about 150 atomic mass units; g)1,1,1-trifluoroalkanes represented by the formula CF₃R¹, wherein R¹ isselected from aliphatic and alicyclic hydrocarbon radicals having fromabout 5 to about 15 carbon atoms; h) fluoroethers represented by theformula R¹OCF₂CF₂H, wherein R¹ is selected from aliphatic, alicyclic,and aromatic hydrocarbon radicals having from about 5 to about 15 carbonatoms; or wherein said fluoroethers are derived from fluoroolefins andpolyols, wherein said fluoroolefins are of the type CF₂═CXY, wherein Xis hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF₃ orOR_(f), wherein R_(f) is CF₃, C2F5, or C₃F₇; and said polyols are linearor branched, wherein said linear polyols are of the typeHOCH₂(CHOH)_(x)(CRR′)_(y)CH₂OH, wherein R and R′ are hydrogen, CH₃ orC₂H₅, x is an integer from 0-4, y is an integer from 0-3 and z is eitherzero or 1, and said branched polyols are of the typeC(OH)_(t)(R)_(u)(CH₂OH)_(v)[(CH₂)_(m),CH₂OH]_(w), wherein R may behydrogen, CH₃ or C₂H₅, m is an integer from 0 to 3, t and u are 0 or 1,v and w are integers from 0 to 4, and also wherein t+u+v+w=4; and i)lactones represented by structures [B], [C], and [D]:

 wherein, R₁ through R₈ are independently selected from hydrogen,linear, branched, cyclic, bicyclic, saturated and unsaturatedhydrocarbyl radicals; and the molecular weight is from about 100 toabout 300 atomic mass units; and j) esters represented by the generalformula R¹CO₂R², wherein R¹ and R² are independently selected fromlinear and cyclic, saturated and unsaturated, alkyl and aryl radicals;and wherein said esters have a molecular weight of from about 80 toabout 550 atomic mass units.
 4. The composition of claim 3, furthercomprising a stabilizer or odor masking agent.
 5. The composition ofclaim 4, wherein said stabilizer is selected from the group consistingof nitromethane, hindered phenols, hydroxylamines, thiols, phosphitesand lactones.
 6. A method for improving oil-return to the compressor ina compression refrigeration, air-conditioning or heat pump apparatus,said method comprising using the composition of claim 3 in saidapparatus.
 7. The composition of claim 1, further comprising a tracerselected from the group consisting of hydrofluorocarbons, deuteratedhydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons,fluoroethers, brominated compounds, iodated compounds, alcohols,aldehydes, ketones, nitrous oxide (N₂O) and combinations thereof.
 8. Thecomposition of claim 7, wherein said tracer is selected from the groupconsisting of CD₃CD₃, CD₃CD₂CD₃, CD₂F₂, CF₃CD₂CF₃, CD₂FCF₃, CD₃CF₃,CDF₂CF₃, CF₃CDFCF₃, CF₃CF₂CDF₂, CDF₂CDF₂, CF₃CF₂CD₃, CF₃CD₂CH₃,CF₂CH₂CD₃, CF₃CF₃, cyclo-CF₂CF₂CF₂—, CF₃CF₂CF₃, cyclo-CF₂CF₂CF₂CF₂—,CF₃CF₂CF₂CF₃, CF₃CF(CF₃)₂, cyclo-CF(CF₃)CF₂CF(CF₃)CF₂—, CF₃OCHFCF₃,CF₃OCH₂CF₃, CF₃OCH₂CHF₂, CF₃CH₂OCHF₂ CH₃OCF₂CF₃, CH₃CF₂OCF₃CF₃CF₂CF₂OCHFCF₃, CF₃CF₂CF₂OCF(CF₃)CF₂OCHFCF₃, CHF₃, CH₂FCH₃, CHF₂CH₃,CHF₂CHF₂, CF₃CHFCF₃, CF₃CF₂CHF₂, CF₃CF₂CH₂F, CHF₂CHFCF₃, CF₃CH₂CF₃,CF₃CF₂CH₃, CF₃CH₂CHF₂, CHF₂CF₂CH₃, CF₃CHFCH₃, CF₃CH₂CH₃, CH₃CF₂CH₃,CH₃CHFCH₃, CH₂FCH₂CH₃, CHF₂CF₂CF₂CF₃, (CF₃)₂CHCF₃, CF₃CH₂CF₂CF₃,CHF₂CF₂CF₂CHF₂, CH₃CF₂CF₂CF₃, CF₃CHFCHFCF₂CF₃,perfluoromethylcyclopentane, perfluoromethylcyclohexane,perfluorodimethylcyclohexane (ortho, meta, or para),perfluoroethylcyclohexane, perfluoroindan, perfluorotrimethylcyclohexaneand isomers thereof, perfluoroisopropylcyclohexane,cis-perfluorodecalin, trans-perfluorodecalin, cis- ortrans-perfluoromethyldecalin and isomers thereof, CH₃Br, CH₂FBr, CHF₂Br,CHFBr₂, CHBr₃, CH₂BrCH₃, CHBr=CH₂, CH₂BrCH₂Br, CFBr=CHF, CF₃I, CHF₂I,CH₂FI, CF₂ICH₂F, CF₂ICHF₂, CF₂ICF₂I, C₆F₅I, ethanol, n-propanol,isopropanol, acetone, n-propanal, n-butanal, methyl ethyl ketone,nitrous oxide, and combinations thereof.
 9. The composition of claim 1,further comprising at least one ultra-violet fluorescent dye selectedfrom the group consisting of naphthalimides, perylenes, coumarins,anthracenes, phenanthracenes, xanthenes, thioxanthenes,naphthoxanthenes, fluoresceins, derivatives of said dye and combinationsthereof.
 10. The composition of claim 9, further comprising at least onesolubilizing agent selected from the group consisting of hydrocarbons,dimethylether, polyoxyalkylene glycol ethers, amides, ketones, nitriles,chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and1,1,1-trifluoroalkanes.
 11. The composition of claim 10, wherein saidsolubilizing agent is selected from the group consisting of: a)polyoxyalkylene glycol ethers represented by the formulaR¹[(OR²)_(x)OR³]_(y), wherein: x is an integer from 1 to 3; y is aninteger from 1 to 4; R¹ is selected from hydrogen and aliphatichydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R²is selected from aliphatic hydrocarbylene radicals having from 2 to 4carbon atoms; R³ is selected from hydrogen, and aliphatic and alicyclichydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R¹and R³ is selected from said hydrocarbon radicals; and wherein saidpolyoxyalkylene glycol ethers have a molecular weight of from about 100to about 300 atomic mass units; b) amides represented by the formulaeR¹C(O)NR²R³ and cyclo-[R⁴CON(R⁵)-], wherein R¹, R², R³ and R⁵areindependently selected from aliphatic and alicyclic hydrocarbonradicals having from 1 to 12 carbon atoms, and at most one aromaticradical having from 6 to 12 carbon atoms; R⁴ is selected from aliphatichydrocarbylene radicals having from 3 to 12 carbon atoms; and whereinsaid amides have a molecular weight of from about 100 to about 300atomic mass units; c) ketones represented by the formula R¹C(O )R²,wherein R¹ and R² are independently selected from aliphatic, alicyclicand aryl hydrocarbon radicals having from 1 to 12 carbon atoms, andwherein said ketones have a molecular weight of from about 70 to about300 atomic mass units; d) nitriles represented by the formula R¹CN,wherein R¹ is selected from aliphatic, alicyclic or aryl hydrocarbonradicals having from 5 to 12 carbon atoms, and wherein said nitrileshave a molecular weight of from about 90 to about 200 atomic mass units;e) chlorocarbons represented by the formula RCI_(x), wherein; x is 1 or2; R is selected from aliphatic and alicyclic hydrocarbon radicalshaving from 1 to 12 carbon atoms; and wherein said chlorocarbons have amolecular weight of from about 100 to about 200 atomic mass units; f)aryl ethers represented by the formula R¹OR², wherein: R¹ is selectedfrom aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R² isselected from aliphatic hydrocarbon radicals having from 1 to 4 carbonatoms; and wherein said aryl ethers have a molecular weight of fromabout 100 to about 150 atomic mass units; g) 1,1,1-trifluoroalkanesrepresented by the formula CF₃R¹, wherein R¹ is selected from aliphaticand alicyclic hydrocarbon radicals having from about 5 to about 15carbon atoms; h) fluoroethers represented by the formula R¹OCF₂CF₂H,wherein R¹ is selected from aliphatic, alicyclic, and aromatichydrocarbon radicals having from about 5 to about 15 carbon atoms; orwherein said fluoroethers are derived from fluoroolefins and polyols,wherein said fluoroolefins are of the type CF₂═CXY, wherein X ishydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF₃ orOR_(f), wherein R_(f) is CF₃, C₂F₅, or C₃F₇; and said polyols are linearor branched, wherein said linear polyols are of the typeHOCH₂(CHOH)_(x)(CRR′)_(y)CH₂OH, wherein R and R′ are hydrogen, CH₃ orC₂H₅, x is an integer from 0-4, y is an integer from 0-3 and z is eitherzero or 1, and said branched polyols are of the typeC(OH)_(t)(R)_(u)(CH₂OH)_(v)[(CH₂)_(m)CH₂OH]_(w), wherein R may behydrogen, CH₃ or C₂H₅, m is an integer from 0 to 3, t and u are 0 or 1,v and w are integers from 0 to 4, and also wherein t+u+v+w=4; and i)lactones represented by structures [B], [C], and [D]:

 wherein, R₁ through R₈ are independently selected from hydrogen,linear, branched, cyclic, bicyclic, saturated and unsaturatedhydrocarbyl radicals; and the molecular weight is from about 100 toabout 300 atomic mass units; and j) esters represented by the generalformula R¹CO₂R², wherein R¹ and R² are independently selected fromlinear and cyclic, saturated and unsaturated, alkyl and aryl radicals;and wherein said esters have a molecular weight of from about 80 toabout 550 atomic mass units.
 12. A method for detecting the compositionof claim 9 in a compression refrigeration, air conditioning, or heatpump apparatus, said method comprising providing said compositionincluding said ultra-violet fluorescent dye to said apparatus, andproviding a suitable means for detecting said composition at a leakpoint or in the vicinity of said apparatus.
 13. A method of producingcooling, said method comprising: evaporating said composition of claim 1in the vicinity of a body to be cooled and thereafter condensing saidcomposition.
 14. A method of producing heat, said method comprising:condensing said composition of claim 1 in the vicinity of a body to beheated and thereafter evaporating said composition.
 15. A method ofsolubilizing a refrigerant or heat transfer fluid composition comprisingthe composition of claim 1 in a refrigeration lubricant selected fromthe group consisting of mineral oils, alkylbenzenes, syntheticparaffins, synthetic napthenes, and poly(alpha)olefins, wherein saidmethod comprises contacting said lubricant with said composition in thepresence of an effective amount of a compatibilizer, wherein saidcompatibilizer is selected from the group consisting of: a)polyoxyalkylene glycol ethers represented by the formulaR¹[(OR²)_(x)OR³]_(y), wherein: x is an integer from 1 to 3; y is aninteger from 1 to 4; R¹ is selected from hydrogen and aliphatichydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R²is selected from aliphatic hydrocarbylene radicals having from 2 to 4carbon atoms; R³ is selected from hydrogen, and aliphatic and alicyclichydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R¹and R³ is selected from said hydrocarbon radicals; and wherein saidpolyoxyalkylene glycol ethers have a molecular weight of from about 100to about 300 atomic mass units; b) amides represented by the formulaeR¹C(O)NR²R³ and cyclo -[R⁴CON(R⁵)], wherein R¹, R², R³ and R⁵ areindependently selected from aliphatic and alicyclic hydrocarbon radicalshaving from 1 to 12 carbon atoms, and at most one aromatic radicalhaving from 6 to 12 carbon atoms; R⁴ is selected from aliphatichydrocarbylene radicals having from 3 to 12 carbon atoms; and whereinsaid amides have a molecular weight of from about 100 to about 300atomic mass units; c) ketones represented by the formula R¹C(O)R²,wherein R¹ and R² are independently selected from aliphatic, alicyclicand aryl hydrocarbon radicals having from 1 to 12 carbon atoms, andwherein said ketones have a molecular weight of from about 70 to about300 atomic mass units; d) nitriles represented by the formula R¹CN,wherein R¹ is selected from aliphatic, alicyclic or aryl hydrocarbonradicals having from 5 to 12 carbon atoms, and wherein said nitrileshave a molecular weight of from about 90 to about 200 atomic mass units;e) chlorocarbons represented by the formula RCI_(x), wherein; x is 1 or2; R is selected from aliphatic and alicyclic hydrocarbon radicalshaving from 1 to 12 carbon atoms; and wherein said chlorocarbons have amolecular weight of from about 100 to about 200 atomic mass units; f)aryl ethers represented by the formula R¹OR², wherein: R¹ is selectedfrom aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R² isselected from aliphatic hydrocarbon radicals having from 1 to 4 carbonatoms; and wherein said aryl ethers have a molecular weight of fromabout 100 to about 150 atomic mass units; g) 1,1,1-trifluoroalkanesrepresented by the formula CF₃R¹, wherein R¹ is selected from aliphaticand alicyclic hydrocarbon radicals having from about 5 to about 15carbon atoms; h) fluoroethers represented by the formula R¹OCF₂CF₂H,wherein R¹ is selected from aliphatic and alicyclic hydrocarbon radicalshaving from about 5 to about 15 carbon atoms; or wherein saidfluoroethers are derived from fluoro-olefins and polyols, wherein saidfluoro-olefins are of the type CF₂═CXY, wherein X is hydrogen, chlorineor fluorine, and Y is chlorine, fluorine, CF₃ or OR_(f), wherein R_(f)is CF₃, C₂F₅, or C₃F₇; and said polyols are of the typeHOCH₂CRR′(CH₂)_(z)(CHOH)_(x)CH₂(CH₂OH)_(y), wherein R and R′ arehydrogen, CH₃ or C₂H₅, x is an integer from 0-4, y is an integer from0-3 and z is either zero or 1; and i) lactones represented by structures[B], [C], and [D]:

 wherein, R₁ through R₈ are independently selected from hydrogen,linear, branched, cyclic, bicyclic, saturated and unsaturatedhydrocarbyl radicals; and the molecular weight is from about 100 toabout 300 atomic mass units; and j) esters represented by the generalformula R¹CO₂R², wherein R¹ and R² are independently selected fromlinear and cyclic, saturated and unsaturated, alkyl and aryl radicals;and wherein said esters have a molecular weight of from about 80 toabout 550 atomic mass units.
 16. A method for replacing a high GWPrefrigerant in a refrigeration, air-conditioning, or heat pumpapparatus, wherein said high GWP refrigerant is selected from the groupconsisting of R134a, R22, R123, R11, R245fa, R114, R236fa, R124, R12,R410A, R407C, R417A, R422A, R507A, R502, and R404A, said methodcomprising providing the composition of claim 1 to said refrigeration,air-conditioning, or heat pump apparatus that uses, used or is designedto use said high GWP refrigerant.
 17. A method of using the compositionof claim 1 as a heat transfer fluid composition, said process comprisingtransporting said composition from a heat source to a heat sink.
 18. Arefrigeration, air-conditioning, or heat pump apparatus containing acomposition as claimed in claim
 1. 19. The apparatus of claim 18comprising a mobile apparatus.
 20. The apparatus of claim 19 comprisingan automobile air-conditioning apparatus.
 21. The apparatus of claim 19comprising refrigerated road transport equipment.
 22. The apparatus ofclaim 18 comprising a stationary air-conditioning system.
 23. Theapparatus of claim 18 comprising a stationary heat pump system.
 24. Theapparatus of claim 18 comprising a stationary refrigeration system. 25.A method of forming a foam comprising: a) adding to a foamablecomposition the composition of claim 1; and b) reacting the foamablecomposition under conditions effective to form a foam.
 26. A process forproducing aerosol products comprising the step of adding the compositionof claim 1 to active ingredients in an aerosol container, wherein saidcomposition functions as a propellant.
 27. An azeotropic ornear-azeotropic composition comprising about 71 weight percent to about99 weight percent HFC-1234yf and about 29 weight percent to about 1weight percent n-butane.
 28. The composition of claim 27 wherein thecomposition is an azeotropic composition comprising about 98.1 weightpercent HFC-1234yf and about 1.9 weight percent n-butane at a pressureof 17.9 psi (123 kPa) and a temperature of −25° C.
 29. An azeotropic ornear-azeotropic composition consisting essentially of HFC-1234yf andn-butane.
 30. The azeotropic or near-azeotropic composition of claim 29consisting of HFC-1234yf and n-butane.